Polymers Produced via Use of Quinolinyldiamido Transition Metal Complexes and Vinyl Transfer Agents

ABSTRACT

Catalyst systems with single site transition metal complexes (such as quinolinyldiamide transition metal complexes), an activator, and a metal hydrocarbenyl transfer agent (preferably an aluminum vinyl-transfer agent) are disclosed for use in alkene polymerization.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority to and the benefit of U.S. Ser. No.62/464,933, filed Feb. 28, 2017 and is incorporated by reference in itsentirety.

This application is a Continuation-in-Part of U.S. Ser. No. 15/629,586,filed Jun. 21, 2017, which claims priority to and the benefit of U.S.Ser. No. 62/357,033, filed Jun. 30, 2016.

This application relates to U.S. Ser. No. 62/212,405, filed Aug. 31,2015; U.S. Ser. No. 62/332,940, filed May 6, 2016; and U.S. Ser. No.62/332,921, also filed May 6, 2016.

FIELD OF THE INVENTION

The invention relates to the use of quinolinyldiamido transition metalcomplexes and catalyst systems with an activator and a metalhydrocarbenyl chain transfer agent, such as an aluminum vinyl-transferagent (AVTA).

BACKGROUND OF THE INVENTION

Pyridyl amines have been used to prepare Group 4 complexes which areuseful transition metal components for the polymerization of alkenes,see for example US 2002/0142912; U.S. Pat. No. 6,900,321; and U.S. Pat.No. 6,103,657, where the ligands have been used in complexes in whichthe ligands are coordinated in a bidentate fashion to the transitionmetal atom.

WO 2005/095469 shows catalyst compounds that use tridentate ligandsthrough two nitrogen atoms (one amido and one pyridyl) and one oxygenatom.

US 2004/0220050A1 and WO 2007/067965 disclose complexes in which theligand is coordinated in a tridentate fashion through two nitrogen (oneamido and one pyridyl) and one carbon (aryl anion) donor.

A key step in the activation of these complexes is the insertion of analkene into the metal-aryl bond of the catalyst precursor (Froese, R. D.J. et al., J. Am. Chem. Soc. 2007, 129, pp. 7831-7840) to form an activecatalyst that has both a five-membered and a seven-membered chelatering.

WO 2010/037059 discloses pyridine containing amines for use inpharmaceutical applications.

U.S. Pat. No. 8,158,733 describes catalyst compositions featuring2-(2-aryloxy)-8-anilinoquinoline, 2,8-bis(2-aryloxy)quinoline, and2,8-bis(2-aryloxy)dihydroquinoline ligands that do not feature atridentate NNN donor ligand.

US 2012/0016092 describes catalyst compositions containing2-imino-8-anilinoquinoline and 2-aminoalkyl-8-anilinoquinoline ligandshaving a one-atom linker between the quinoline and the nitrogen donor atthe 2-position of the quinoline ring.

US 2010/0227990 A1 discloses ligands that bind to the metal center witha NNC donor set instead of an NNN or NNP donor set.

WO 2002/38628 A2 discloses ligands that bind to the metal center with aNNC donor set instead of an NNN or NNP donor set.

WO 2016/102690 discloses a process for preparation of a branchedpolyolefin using a metal hydrocarbyl transfer agent.

Organometallics, 2012, 31, p. 3241 by Hu et al. describes catalystcompositions containing 2-aminoalkyl-8-quinolinolato ligands that do notfeature a tridentate NNN donor ligand.

Organometallics, 2013, 32, p. 2685 by Nifant'ev et al. describescatalyst compositions containing 2,8-bis(2-aryloxy)dihydroquinolineligands that do not feature a tridentate NNN donor ligand.

Dalton Transactions, 2013, 42, p. 1501 by Nifant'ev et al. describescatalyst compositions containing 2-aryl-8-arylaminoquinoline ligandsthat do not feature a tridentate NNN donor ligand.

U.S. Pat. No. 7,858,718 describes catalyst compositions containing2-aryl-8-anilinoquinoline ligands that do not feature a tridentate NNNdonor ligand.

U.S. Pat. No. 7,973,116 describes catalyst compositions containingpyridyldiamide ligands, e.g., a pyridine-based ligand not aquinoline-based ligand.

US 2014/0256893 discloses the use of chain transfer agents, such asdiethyl zinc, with transition metal pyridyldiamide catalysts inpolymerization processes.

Guerin, F.; McConville, D. H.; Vittal, J. J., Organometallics, 1996, 15,p. 5586, discloses a ligand family and group 4 complexes that use aNNN-donor set, but do not feature seven-membered chelate ring or eitherof dihydroindenyl- and tetrahydronaphthalenyl-groups.

Macromolecules, 2002, 35, 6760-6762 discloses propene polymerizationwith tetrakis(pentafluorophenyl)borate, 7-octenyldiisobutylaluminum, andracMe₂Si(2-Me-indenyl)₂ZrCl₂ or Ph₂C(cyclopentadienyl)(fluorenyl)ZrCl₂to produce polypropylene with octenyldiisobutylaluminum incorporated asa comonomer.

U.S. Pat. No. 7,973,116; U.S. Pat. No. 8,394,902; US 2011-0224391; US2011-0301310 A1; and U.S. Ser. No. 61/815,065, filed Apr. 23, 2013,disclose pyridylamido transition metal complexes that do not featuredihydroindenyl- or tetrahydronaphthalenyl-groups.

References of interest also include: 1) Vaughan, A; Davis, D. S.;Hagadorn, J. R. in Comprehensive Polymer Science, Vol. 3, Chapter 20,“Industrial catalysts for alkene polymerization”; 2) Gibson, V. C.;Spitzmesser, S. K. Chem. Rev. 2003, 103, 283; 3) Britovsek, G. J. P.;Gibson, V. C.; Wass, D. F. Angew. Chem. Int. Ed. 1999, 38, 428; 4) US2011/021727; and 5) Zhang, et al., Tetrahedron, Vol. 69, No. 49, Dec. 1,2013, pages 10644-10652.

There is still a need in the art for new and improved catalyst systemsfor the polymerization of olefins, in order to achieve specific polymerproperties, such as long chain branching, high melting point, highmolecular weights, to increase conversion or comonomer incorporation, orto alter comonomer distribution without deteriorating the resultingpolymer's properties.

SUMMARY OF THE INVENTION

This invention relates to catalyst systems comprising an activator,metal hydrocarbenyl chain transfer agent (such as an aluminumvinyl-transfer agent), and single site catalyst complex, such as aquinolinyldiamido and related transition metal complexes represented bythe Formula (I) or (II):

wherein:M is a Group 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 metal;J is a three-atom-length bridge between the quinoline and the amidonitrogen;E is selected from carbon, silicon, or germanium;X is an anionic leaving group;L is a neutral Lewis base;R¹ and R¹³ are independently selected from the group consisting ofhydrocarbyls, substituted hydrocarbyls, and silyl groups;R² through R¹² are independently selected from the group consisting ofhydrogen, hydrocarbyls, alkoxy, silyl, amino, aryloxy, substitutedhydrocarbyls, halogen, and phosphino;n is 1 or 2;m is 0, 1, or 2n+m is not greater than 4; andany two adjacent R groups (e.g., R¹ & R², R² & R³, etc.) may be joinedto form a substituted or unsubstituted hydrocarbyl or heterocyclic ring,where the ring has 5, 6, 7, or 8 ring atoms and where substitutions onthe ring can join to form additional rings;any two X groups may be joined together to form a dianionic group;any two L groups may be joined together to form a bidentate Lewis base;andan X group may be joined to an L group to form a monoanionic bidentategroup.

This invention further relates to catalyst systems comprising activator,transition metal catalyst complex represented by the Formula (I) or (II)above, and aluminum vinyl transfer agent represented by formula:

Al(R′)_(3-v)(R″)_(v)

wherein each R′, independently, is a C₁-C₃₀ hydrocarbyl group; each R″,independently, is a C₄-C₂₀ hydrocarbenyl group having an end-vinylgroup; and v is from 0.1 to 3.

This invention further relates to processes to produce the abovecatalyst systems and methods to polymerize olefins using the abovecatalyst systems.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph of EP copolymers: wt. % propylene vs. polymer Mn forexamples EP-13, 14, 15, 25, 27, 32, 37, 38, 39 (black markers) vs.comparative examples from 2015EM149, EP-13, 15, 17, 19, 22, 23, 25, 27,29 (gray markers).

FIG. 2 is a graph of EP copolymers: Aluminum vinyl transfer agent (AVTA)concentration in micromoles vs. polymer Mn for examples EP-13 to EP-48(black markers) vs. comparative examples from 2015EM149, EP-13 to EP-48(gray markers).

FIG. 3 is a graph of EP copolymers: Aluminum vinyl transfer agent (AVTA)concentration in micromoles vs. polymer g′(vis) from GPC 3D for examplesEP-13, 14, 15, 18, 25, 27, 28, 29, 30, 32, 37, 38, 39, 40, 41, 42 fromTable 3 (black markers) vs. comparative examples from 2015EM149, EP-15,17, 19, 22, 23, 25, 27, 29, 35, 39, 43, 45 from table 10 (gray markers).

DETAILED DESCRIPTION OF THE INVENTION

The specification describes transition metal complexes and catalystsystems that include the transition metal complexes. The term complex isused to describe molecules in which an ancillary ligand is coordinatedto a central transition metal atom. The ligand is bulky and stablybonded to the transition metal so as to maintain its influence duringuse of the catalyst, such as polymerization. The ligand may becoordinated to the transition metal by covalent bond and/or electrondonation coordination or intermediate bonds. The transition metalcomplexes are generally subjected to activation to perform theirpolymerization or oligomerization function using an activator which isbelieved to create a cation as a result of the removal of an anionicgroup, often referred to as a leaving group, from the transition metal.

As used herein, the numbering scheme for the Periodic Table groups isthe new notation as set out in Chemical and Engineering News, 63(5), 27(1985).

“Catalyst productivity” is a measure of how many grams of polymer (P)are produced using a polymerization catalyst comprising W g of catalyst(cat), over a period of time of T hours; and may be expressed by thefollowing formula: P/(T×W) and expressed in units of gPgcat⁻¹ hr⁻¹.Conversion is the amount of monomer that is converted to polymerproduct, and is reported as mol % and is calculated based on the polymeryield and the amount of monomer fed into the reactor. Catalyst activityis a measure of how active the catalyst is and is reported as the massof product polymer (P) produced per mole of catalyst (cat) used(kgP/molcat).

An “olefin,” alternatively referred to as “alkene,” is a linear,branched, or cyclic compound of carbon and hydrogen having at least onedouble bond. For purposes of this specification and the claims appendedthereto, when a polymer or copolymer is referred to as comprising anolefin, the olefin present in such polymer or copolymer is thepolymerized form of the olefin. For example, when a copolymer is said tohave an “ethylene” content of 35 wt % to 55 wt %, it is understood thatthe mer unit in the copolymer is derived from ethylene in thepolymerization reaction and said derived units are present at 35 wt % to55 wt %, based upon the weight of the copolymer. A “polymer” has two ormore of the same or different mer units. A “homopolymer” is a polymerhaving mer units that are the same. A “copolymer” is a polymer havingtwo or more mer units that are different from each other. A “terpolymer”is a polymer having three mer units that are different from each other.“Different” as used to refer to mer units indicates that the mer unitsdiffer from each other by at least one atom or are differentisomerically. Accordingly, the definition of copolymer, as used herein,includes terpolymers and the like. An “ethylene polymer” or “ethylenecopolymer” is a polymer or copolymer comprising at least 50 mol %ethylene derived units, a “propylene polymer” or “propylene copolymer”is a polymer or copolymer comprising at least 50 mol % propylene derivedunits, and so on. An oligomer is typically a polymer having a lowmolecular weight, such as an Mn of less than 25,000 g/mol, or in anembodiment less than 2,500 g/mol, or a low number of mer units, such as75 mer units or less or 50 mer units or less. An “ethylene polymer” or“ethylene copolymer” is a polymer or copolymer comprising at least 50mol % ethylene derived units, a “propylene polymer” or “propylenecopolymer” is a polymer or copolymer comprising at least 50 mol %propylene derived units, and so on.

For the purposes of this invention, ethylene shall be considered anα-olefin.

For purposes of this invention and claims thereto, the term“substituted” means that a hydrogen group has been replaced with aheteroatom, or a heteroatom-containing group. For example, a“substituted hydrocarbyl” is a radical made of carbon and hydrogen whereat least one hydrogen is replaced by a heteroatom orheteroatom-containing group.

As used herein, M_(n) is number average molecular weight, M_(w) isweight average molecular weight, and M_(z) is z average molecularweight, wt % is weight percent, and mol % is mole percent. Molecularweight distribution (MWD), also referred to as polydispersity index(PDI), is defined to be M_(w) divided by M_(n). Unless otherwise noted,all molecular weight units (e.g., M_(w), M_(n), M_(z)) are g/mol.

Unless otherwise noted all melting points (Tm) are DSC second melt.

The following abbreviations may be used herein: dme is1,2-dimethoxyethane, Me is methyl, Ph is phenyl, Et is ethyl, Pr ispropyl, iPr is isopropyl, n-Pr is normal propyl, Bu is butyl, cPR iscyclopropyl, iBu is isobutyl, tBu is tertiary butyl, p-tBu ispara-tertiary butyl, nBu is normal butyl, sBu is sec-butyl, TMS istrimethylsilyl, TIBAL is triisobutylaluminum, TNOAL istri(n-octyl)aluminum, MAO is methylalumoxane, p-Me is para-methyl, Ph isphenyl, Bn is benzyl (i.e., CH₂Ph), THF (also referred to as thf) istetrahydrofuran, RT is room temperature (and is 23° C. unless otherwiseindicated), tol is toluene, EtOAc is ethyl acetate, Cy is cyclohexyl andAVTA is an aluminum-based vinyl transfer agent.

A “catalyst system” comprises at least one catalyst compound and atleast one activator. When “catalyst system” is used to describe such thecatalyst compound/activator combination before activation, it means theunactivated catalyst complex (pre-catalyst) together with an activatorand, optionally, a co-activator. When it is used to describe thecombination after activation, it means the activated complex and theactivator or other charge-balancing moiety. The transition metalcompound may be neutral as in a pre-catalyst, or a charged species witha counter ion as in an activated catalyst system. For the purposes ofthis invention and the claims thereto, when catalyst systems aredescribed as comprising neutral stable forms of the components, it iswell understood by one of ordinary skill in the art, that the ionic formof the component is the form that reacts with the monomers to producepolymers.

In the description herein, the catalyst may be described as a catalystprecursor, pre-catalyst compound, catalyst compound, transition metalcomplex, or transition metal compound, and these terms are usedinterchangeably. A polymerization catalyst system is a catalyst systemthat can polymerize monomers to polymer. An “anionic ligand” is anegatively charged ligand which donates one or more pairs of electronsto a metal ion. A “neutral donor ligand” is a neutrally charged ligandwhich donates one or more pairs of electrons to a metal ion. Activatorand cocatalyst are also used interchangeably.

A scavenger is a compound that is typically added to facilitatepolymerization by scavenging impurities. Some scavengers may also act asactivators and may be referred to as co-activators. A co-activator, thatis not a scavenger, may also be used in conjunction with an activator inorder to form an active catalyst. In some embodiments a co-activator canbe pre-mixed with the transition metal compound to form an alkylatedtransition metal compound.

Noncoordinating anion (NCA) is defined to mean an anion either that doesnot coordinate to the catalyst metal cation or that does coordinate tothe metal cation, but only weakly. The term NCA is also defined toinclude multicomponent NCA-containing activators, such asN,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, that contain anacidic cationic group and the non-coordinating anion. The term NCA isalso defined to include neutral Lewis acids, such astris(pentafluorophenyl)boron, that can react with a catalyst to form anactivated species by abstraction of an anionic group. An NCA coordinatesweakly enough that a neutral Lewis base, such as an olefinically oracetylenically unsaturated monomer can displace it from the catalystcenter. Any metal or metalloid that can form a compatible, weaklycoordinating complex may be used or contained in the noncoordinatinganion. Suitable metals include, but are not limited to, aluminum, gold,and platinum. Suitable metalloids include, but are not limited to,boron, aluminum, phosphorus, and silicon. Activators containingnon-coordinating anions can also be referred to as stoichiometricactivators. A stoichiometric activator can be either neutral or ionic.The terms ionic activator and stoichiometric ionic activator can be usedinterchangeably. Likewise, the terms neutral stoichiometric activatorand Lewis acid activator can be used interchangeably. The termnon-coordinating anion activator includes neutral stoichiometricactivators, ionic stoichiometric activators, ionic activators, and Lewisacid activators.

For purposes of this invention and claims thereto in relation tocatalyst compounds, the term “substituted” means that a hydrogen grouphas been replaced with a hydrocarbyl group, a heteroatom, or aheteroatom-containing group. For example, methyl cyclopentadiene (Cp) isa Cp group substituted with a methyl group.

For purposes of this invention and claims thereto, “alkoxides” includethose where the alkyl group is a C₁ to C₁₀ hydrocarbyl. The alkyl groupmay be straight chain, branched, or cyclic. The alkyl group may besaturated or unsaturated. In some embodiments, the alkyl group maycomprise at least one aromatic group.

The terms “hydrocarbyl radical,” “hydrocarbyl,” “hydrocarbyl group,”“alkyl radical,” and “alkyl” are used interchangeably throughout thisdocument. Likewise, the terms “group,” “radical,” and “substituent” arealso used interchangeably in this document. For purposes of thisdisclosure, “hydrocarbyl radical” is defined to be C1-C100 radicals,that may be linear, branched, or cyclic, and when cyclic, aromatic ornon-aromatic. Examples of such radicals include, but are not limited to,methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl,tert-butyl, pentyl, iso-amyl, hexyl, octyl cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl, cyclooctyl, and the like including theirsubstituted analogues. Substituted hydrocarbyl radicals are radicals inwhich at least one hydrogen atom of the hydrocarbyl radical has beensubstituted with at least one halogen (such as Br, Cl, F or I) or atleast one functional group such as NR*₂, OR*, SeR*, TeR*, PR*₂, AsR*₂,SbR*₂, SR*, BR*₂, SiR*₃, GeR*₃, SnR*₃, PbR*₃, and the like, or where atleast one heteroatom has been inserted within a hydrocarbyl ring.

The term “alkenyl” means a straight-chain, branched-chain, or cyclichydrocarbon radical having one or more double bonds. These alkenylradicals may, optionally, be substituted. Examples of suitable alkenylradicals include, but are not limited to, ethenyl, propenyl, allyl,1,4-butadienyl cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl,cycloctenyl, and the like, including their substituted analogues.

The term “alkoxy” or “alkoxide” means an alkyl ether or aryl etherradical wherein the term alkyl is as defined above. Examples of suitablealkyl ether radicals include, but are not limited to, methoxy, ethoxy,n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy,phenoxyl, and the like.

The term “aryl” or “aryl group” means a six carbon aromatic ring and thesubstituted variants thereof, including but not limited to, phenyl,2-methyl-phenyl, xylyl, 4-bromo-xylyl. Likewise, heteroaryl means anaryl group where a ring carbon atom (or two or three ring carbon atoms)has been replaced with a heteroatom, preferably N, O, or S. As usedherein, the term “aromatic” also refers to pseudoaromatic heterocycleswhich are heterocyclic substituents that have similar properties andstructures (nearly planar) to aromatic heterocyclic ligands, but are notby definition aromatic; likewise the term aromatic also refers tosubstituted aromatics.

Where isomers of a named alkyl, alkenyl, alkoxide, or aryl group exist(e.g., n-butyl, iso-butyl, sec-butyl, and tert-butyl) reference to onemember of the group (e.g., n-butyl) shall expressly disclose theremaining isomers (e.g., iso-butyl, sec-butyl, and tert-butyl) in thefamily. Likewise, reference to an alkyl, alkenyl, alkoxide, or arylgroup without specifying a particular isomer (e.g., butyl) expresslydiscloses all isomers (e.g., n-butyl, iso-butyl, sec-butyl, andtert-butyl).

The term “ring atom” means an atom that is part of a cyclic ringstructure. By this definition, a benzyl group has six ring atoms andtetrahydrofuran has 5 ring atoms.

A heterocyclic ring is a ring having a heteroatom in the ring structureas opposed to a heteroatom substituted ring where a hydrogen on a ringatom is replaced with a heteroatom. For example, tetrahydrofuran is aheterocyclic ring and 4-N,N-dimethylamino-phenyl is a heteroatomsubstituted ring.

The term “continuous” means a system that operates without interruptionor cessation. For example, a continuous process to produce a polymerwould be one where the reactants are continually introduced into one ormore reactors and polymer product is continually withdrawn.

A solution polymerization means a polymerization process in which thepolymer is dissolved in a liquid polymerization medium, such as an inertsolvent or monomer(s) or their blends. A solution polymerization istypically homogeneous. A homogeneous polymerization is one where thepolymer product is dissolved in the polymerization medium. Such systemsare preferably not turbid as described in J. Vladimir Oliveira, C.Dariva and J. C. Pinto, Ind. Eng. Chem. Res., 29, 2000, 4627.

A bulk polymerization means a polymerization process in which themonomers and/or comonomers being polymerized are used as a solvent ordiluent using little or no inert solvent as a solvent or diluent. Asmall fraction of inert solvent might be used as a carrier for catalystand scavenger. A bulk polymerization system contains less than 25 wt %of inert solvent or diluent, preferably less than 10 wt %, preferablyless than 1 wt %, preferably 0 wt %.

This invention relates to catalyst systems comprising aquinolinyldiamide transition metal complex represented by the formula(I) or (II), an activator (such as an alumoxane or a non-coordinatinganion), and metal hydrocarbenyl transfer agent, typically represented bythe formula: Al(R′)_(3-v)(R″)_(v), wherein each R′, independently, is aC₁ to C₃₀ hydrocarbyl group; each R″, independently, is a C₄ to C₂₀hydrocarbenyl group having an allyl chain end; v is from 0.01 to 3 (suchas 1 or 2). Preferably, the metal hydrocarbenyl transfer agent is analuminum vinyl-transfer agent (AVTA) represented by the formula:Al(R′)_(3-v)(R)_(v) with R defined as a hydrocarbenyl group containing 4to 20 carbon atoms and featuring an allyl chain end, R′ defined as ahydrocarbyl group containing 1 to 30 carbon atoms, and v defined as 0.1to 3 (such as 1 or 2).

The catalyst/activator combinations are formed by combining thetransition metal complex with activators in any manner known from theliterature, including by supporting them for use in slurry or gas phasepolymerization. The catalyst/activator combinations may also be added toor generated in solution polymerization or bulk polymerization (in themonomer). The metal hydrocarbenyl transfer agent (preferably an aluminumvinyl transfer agent) may be added to the catalyst and or activatorbefore, during or after the activation of the catalyst complex or beforeor during polymerization. Typically, the metal hydrocarbenyl transferagent (preferably the aluminum vinyl-transfer agent) is added to thepolymerization reaction separately, such as before, thecatalyst/activator pair.

The polymer produced from the polymerization using the catalyst systemsdescribed herein preferably contains at least one allyl chain end.Ethylene homopolymers and copolymers are particularly preferredproducts. If the catalyst complex chosen is also capable ofincorporating bulky alkene monomers, such as C₆ to C₂₀ alpha olefins,into the growing polymer chain, then the resulting polymer (typically anethylene copolymer) may contain long chain branches formed by theinsertion of an allyl terminated polymer chain formed in situ (alsoreferred to as a “vinyl-terminated macromonomer”) into the growingpolymer chains. Process conditions including residence time, the ratioof monomer to polymer in the reactor, and the ratio of transfer agent topolymer will affect the amount of long chain branching in the polymer,the average length of branches, and the type of branching observed. Avariety of branching types may be formed, which include combarchitectures and branch on branch structures similar to those found inlow-density polyethylene. The combination of chain growth andvinyl-group insertion may lead to polymer with a branched structure andhaving one or fewer vinyl unsaturations per polymer molecule. Theabsence of significant quantities of individual polymer moleculescontaining greater than one vinyl unsaturation prevents or reduces theformation of unwanted crosslinked polymers. Polymers having long chainbranching typically have a g′vis of 0.90 or less, alternately 0.85 orless, alternately 0.80 or less, alternately 0.75 or less, alternately0.70 or less, alternately 0.60 or less.

If the catalyst chosen is poor at incorporating comonomers such as C₂ toC₂₀ alpha olefins, then the polymer obtained is largely linear (littleor no long chain branching). Likewise, process conditions including theratio of transfer agent to polymer will affect the molecular weight ofthe polymer. Polymers having little or no long chain branching typicallyhave a g′vis of more than 0.90, alternately 0.95 or more, alternately0.98 or more.

Alkene polymerizations and co-polymerizations using one or more transferagents, such as an AVTA, with two or more catalysts are also ofpotential use. Desirable products that may be accessed with thisapproach includes polymers that have branch block structures and/or highlevels of long-chain branching.

The transfer agent to catalyst complex equivalence ratio can be fromabout 1:100 to 500,000:1. Preferably, the molar ratio of transfer agentto catalyst complex is greater than one. Alternately, the molar ratio oftransfer agent to catalyst complex is greater than 30. The AVTA tocatalyst complex equivalence ratio can be from about 1:100 to 500,000:1.Preferably, the molar ratio of AVTA to catalyst complex is greater thanone. More preferred, the molar ratio of AVTA to catalyst complex isgreater than 30.

The AVTA can also be used in combination with other chain transferagents that are typically used as scavengers, such as trialkyl aluminumcompounds (where the alkyl groups are selected from C₁ to C₂₀ alkylgroups, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, nonyl, decyl, undecyl, dodecyl, or an isomer thereof). Usefully,the ATVA can be used in combination with a trialkyl aluminum compoundsuch as tri-n-octylaluminum and triisobutylaluminum.

The transfer agent can also be used in combination withoxygen-containing organoaluminums such as bis(diisobutylaluminum)oxide,MMAO-3A, and other alumoxanes. Certain of these oxygen-containingorganoaluminums are expected to serve as scavengers while remainingsignificantly less prone to hydrocarbyl group chain-transfer thantypical organoaluminums, such as trimethylaluminum ortri(n-octyl)aluminum.

The production of di-end-functionalized polymers is possible with thistechnology. One product, prior to exposure to air, from an alkenepolymerization performed in the presence of AVTA is the aluminum-cappedspecies Al(R′)_(3-v)(polymer-CH═CH₂)_(v), where v is 0.1 to 3(alternately 1 to 3, alternately 1, 2, or 3). The Al-carbon bonds willreact with a variety of electrophiles (and other reagents), such asoxygen, halogens, carbon dioxide, and the like. Thus, quenching thereactive polymer mixture with an electrophile prior to exposure toatmosphere would yield a di-end-functionalized product of the generalformula: Z-(monomers)_(n)-CH═CH₂, where Z is a group from the reactionwith the electrophile and n is an integer, such as from 1 to 1,000,000,alternately from 2 to 50,000, alternately from 10 to 25,000. Forexample, quenching with oxygen yields a polymer functionalized at oneend with a hydroxy group and at the other end with a vinyl group.Quenching with bromine yields a polymer functionalized at one end with aBr group and at the other end with a vinyl group.

Functional group terminated polymers can also be produced usingfunctional group transfer agents (FGTA). In this embodiment of theinvention, the FGTA is represented by the formulaM^(FGTA)(R′)_(3-v)(FG)_(v), with R′ and v defined as above, M^(FGTA) agroup 13 element (such as B or Al), and with FG defined as a groupcontaining 1 to 20 carbon atoms and a functional group Z. The choice ofFG is such that it is compatible with the catalyst system being used.Preferred Z groups include, but are not limited to, non-vinyl olefinicgroups such as vinylidene, vinylene or trisubstituted olefins, cyclicscontaining unsaturation such as cyclohexene, cyclooctene, vinylcyclohexene, aromatics, ethers, and metal-capped alkoxides.

In another embodiment of the invention, the polymer product of thisinvention are of the formula: polymer-(CH₂)_(n)CH═CH₂ where n is from 2to 18, preferably from 6 to 14, more preferably 6, and where “polymer”is the attached polymeryl chain. Polymers of this formula areparticularly well suited in making branch polymer combs. The polymercombs can be made by any number of methods. One method would be to use acatalyst system to make the vinyl terminated polymer, and then use asecond catalyst system to incorporate the vinyl terminated polymer intoa polymer backbone made from the second catalyst. This can be donesequentially in one reactor by first making the vinyl terminated polymerand then adding a second catalyst and, optionally, different monomerfeeds in the same reactor. Alternatively, two reactors in series can beused where the first reactor is used to make the vinyl terminatedpolymer which flows into a second reactor in series having the secondcatalyst and, optionally, different monomer feeds. The vinyl terminatedpolymer can be a soft material, as in an ethylene propylene copolymer(such as ethylene propylene copolymer rubber), low density polyethylene,or a polypropylene, or a harder material, as in an isotacticpolypropylene, high density polyethylene, or other polyethylene.Typically, if the vinyl terminated polymer is soft, it is preferred thatthe polymer backbone of the comb be hard; if the vinyl terminatedpolymer is hard, it is preferred that the polymer backbone of the combbe soft; however, any combination of polymer structures and types can beused.

In another embodiment of the invention, the vinyl-terminated polymers(VTPs) of this invention are of formula: polymer-(CH₂)_(n)CH═CH₂ where nis from 2 to 18, preferably from 6 to 14, more preferably 6 to 8,preferably 6 or 8, and where “polymer” is the attached polymeryl chain.VTPs of this formula are particularly well suited in making branch blockpolymers. The branch block polymers can be made by any number ofmethods. One method involves using the same catalyst that is used tomake the VTP, and then changing polymerization conditions (such as, butnot limited to, by changing monomer composition and/or type and/or theamount or presence of AVTA) in the same or different reactor (such astwo or more reactors in series). In this case, the branch will have adifferent polymeric composition vs. the polymer backbone created underthe different polymerization conditions. Another method would be to usea catalyst system to make the VTP, then use a second catalyst system toincorporate the VTPs into a polymer backbone made from the secondcatalyst. This can be done sequentially in one reactor by first makingthe VTP and then adding a second catalyst and, optionally, differentmonomer feeds in the same reactor. Alternatively, two reactors in seriescan be used where the first reactor is used to make the VTP which flowsinto a second reactor in series having the second catalyst and,optionally, different monomer feeds. The branched block polymers can beof any composition; however, typically, a combination of soft and hardpolymers (relative to one another) are preferred. For example, an iPPVTP could be produced in a reactor, and then ethylene added to theexisting propylene feed to make a rubber EP that would have iPPbranches. Or an iPP VTP could be produced in a first reactor, and thensent to a second reactor containing ethylene (or additional ethylene fora propylene ethylene copolymer and, optionally, additional propylenemonomer (and the same or different catalyst) to make a rubber EP thatwould have iPP branches (or propylene ethylene copolymer branches).

Useful metal hydrocarbenyl transfer agents (preferably the aluminumvinyl transfer agents) are typically present at from 10 or 20 or 50 or100 equivalents to 600 or 700 or 800 or 1000 equivalents relative to thecatalyst complex. Alternately, the metal hydrocarbenyl transfer agentsare present at a catalyst complex-to-transfer agent molar ratio of fromabout 1:3000 to 10:1; alternatively 1:2000 to 10:1; alternatively 1:1000to 10:1; alternatively, 1:500 to 1:1; alternatively 1:300 to 1:1;alternatively 1:200 to 1:1; alternatively 1:100 to 1:1; alternatively1:50 to 1:1; alternatively 1:10 to 1:1.

In any embodiment of this invention where the aluminum vinyl transferagent is present, the aluminum vinyl transfer agent is present at acatalyst complex-to-aluminum vinyl transfer agent molar ratio of fromabout 1:3000 to 10:1; alternatively 1:2000 to 10:1; alternatively 1:1000to 10:1; alternatively, 1:500 to 1:1; alternatively 1:300 to 1:1;alternatively 1:200 to 1:1; alternatively 1:100 to 1:1; alternatively1:50 to 1:1; alternatively 1:10 to 1:1, alternately from 1:1000 or more.

Transition Metal Complex

Transition metal complexes useful herein include quinolinyldiamidotransition metal complexes where a three-atom linker is used between thequinoline and the nitrogen donor in the 2-position of the quinolinering. This has been found to be an important aspect because the use ofthe three-atom linker is believed to yield a metal complex with aseven-membered chelate ring that is not coplanar with the otherfive-membered chelate ring. The resulting complex is thought to beeffectively chiral (C₁ symmetry), even when there are no permanentstereocenters present. This is a desirable catalyst feature, forexample, for the production of isotactic polyolefins.

Transition metal complexes useful herein include quinolinyldiamidotransition metal complexes represented by Formula (I), preferably byFormula (II):

wherein:M is a Group 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 metal (preferably agroup 4 metal);J is group comprising a three-atom-length bridge between the quinolineand the amido nitrogen, preferably a group containing up to 50non-hydrogen atoms;E is carbon, silicon, or germanium;X is an anionic leaving group, (such as a hydrocarbyl group or ahalogen);L is a neutral Lewis base;R¹ and R¹³ are independently selected from the group consisting ofhydrocarbyls, substituted hydrocarbyls, and silyl groups;R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² are independentlyhydrogen, hydrocarbyl, alkoxy, silyl, amino, aryloxy, substitutedhydrocarbyl, halogen, or phosphino;n is 1 or 2;m is 0, 1, or 2, wheren+m is not greater than 4; andany two adjacent R groups (e.g., R¹ & R², R² & R³, etc.) may be joinedto form a substituted hydrocarbyl, unsubstituted hydrocarbyl,substituted heterocyclic ring, or unsubstituted heterocyclic ring, wherethe ring has 5, 6, 7, or 8 ring atoms and where substitutions on thering can join to form additional rings;any two X groups may be joined together to form a dianionic group;any two L groups may be joined together to form a bidentate Lewis base;andany X group may be joined to an L group to form a monoanionic bidentategroup.

Preferably, M is a Group 4 metal, such as zirconium or hafnium.

In a preferred embodiment, J is an aromatic substituted or unsubstitutedhydrocarbyl (preferably a hydrocarbyl) having from 3 to 30 non-hydrogenatoms, preferably J is represented by the formula:

where R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², and E are as defined above, and any twoadjacent R groups (e.g., R⁷ & R⁸, R⁸ & R⁹, R⁹ & R¹⁰ & R¹¹, etc.) may bejoined to form a substituted or unsubstituted hydrocarbyl orheterocyclic ring, where the ring has 5, 6, 7, or 8 ring atoms(preferably 5 or 6 atoms), and said ring may be saturated or unsaturated(such as partially unsaturated or aromatic), preferably J is anarylalkyl (such as arylmethyl, etc.) or dihydro-1H-indenyl, ortetrahydronaphthalenyl group.

In embodiments of the invention, J is selected from the followingstructures:

where

indicates connection to the complex.

In embodiments of the invention, E is carbon.

In embodiments of the invention, X is alkyl (such as alkyl groups having1 to 10 carbons, such as methyl, ethyl, propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, decyl, and isomers thereof), aryl, hydride,alkylsilane, fluoride, chloride, bromide, iodide, triflate, carboxylate,amido (such as NMe₂), or alkylsulfonate.

In embodiments of the invention, L is an ether, amine or thioether.

In embodiments of the invention, R⁷ and R⁸ are joined to form asix-membered aromatic ring with the joined R⁷R⁸ group being—CH═CHCH═CH—.

In embodiments of the invention, R¹⁰ and R¹¹ are joined to form afive-membered ring with the joined R¹⁰R¹¹ group being —CH₂CH₂—.

In embodiments of the invention, R¹⁰ and R¹¹ are joined to form asix-membered ring with the joined R¹⁰R¹¹ group being —CH₂CH₂CH₂—.

In embodiments of the invention, R¹ and R¹³ may be independentlyselected from phenyl groups that are variously substituted with betweenzero to five substituents that include F, Cl, Br, I, CF₃, NO₂, alkoxy,dialkylamino, aryl, and alkyl groups having 1 to 10 carbons, such asmethyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, and isomers thereof.

In a preferred embodiment of the invention, the quinolinyldiamidotransition metal complex represented by the Formula II above where:

M is a Group 4 metal (preferably hafnium);E is selected from carbon, silicon, or germanium (preferably carbon);X is an alkyl, aryl, hydride, alkylsilane, fluoride, chloride, bromide,iodide, triflate, carboxylate, amido, alkoxo, or alkylsulfonate;L is an ether, amine, or thioether;R¹ and R¹³ are independently selected from the group consisting ofhydrocarbyls, substituted hydrocarbyls, and silyl groups (preferablyaryl);R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² are independentlyhydrogen, hydrocarbyl, alkoxy, silyl, amino, aryloxy, substitutedhydrocarbyls, halogen, and phosphino;n is 1 or 2;m is 0, 1, or 2;n+m is from 1 to 4; andtwo X groups may be joined together to form a dianionic group;two L groups may be joined together to form a bidentate Lewis base;an X group may be joined to an L group to form a monoanionic bidentategroup;R⁷ and R⁸ may be joined to form a ring (preferably an aromatic ring, asix-membered aromatic ring with the joined R⁷R group being—CH═CHCH═CH—);R¹⁰ and R¹¹ may be joined to form a ring (preferably a five-memberedring with the joinedR¹⁰R¹¹ group being —CH₂CH₂—, a six-membered ring with the joined R¹⁰R¹¹group being —CH₂CH₂CH₂—).

In embodiments of Formula I and II, R⁴, R⁵, and R⁶ are independentlyselected from the group consisting of hydrogen, hydrocarbyls,substituted hydrocarbyls, alkoxy, aryloxy, halogen, amino, and silyl,and wherein adjacent R groups (R⁴ & R⁵ and/or R⁵ & R⁶) may be joined toform a substituted hydrocarbyl, unsubstituted hydrocarbyl, unsubstitutedheterocyclic ring or substituted heterocyclic ring, where the ring has5, 6, 7, or 8 ring atoms and where substitutions on the ring can join toform additional rings.

In embodiments of Formula I and II, R⁷, R⁸, R⁹, and R¹⁰ areindependently selected from the group consisting of hydrogen,hydrocarbyls, substituted hydrocarbyls, alkoxy, halogen, amino, andsilyl, and wherein adjacent R groups (R⁷ & R⁸, and/or R⁹ & R¹⁰) may bejoined to form a saturated, substituted hydrocarbyl, unsubstitutedhydrocarbyl, unsubstituted heterocyclic ring or substituted heterocyclicring, where the ring has 5, 6, 7, or 8 ring carbon atoms and wheresubstitutions on the ring can join to form additional rings.

In embodiments of Formula I or II, R² and R³ are each, independently,selected from the group consisting of hydrogen, hydrocarbyls, andsubstituted hydrocarbyls, alkoxy, silyl, amino, aryloxy, halogen, andphosphino, R² and R³ may be joined to form a saturated, substituted orunsubstituted hydrocarbyl ring, where the ring has 4, 5, 6, or 7 ringcarbon atoms and where substitutions on the ring can join to formadditional rings, or R² and R³ may be joined to form a saturatedheterocyclic ring, or a saturated substituted heterocyclic ring wheresubstitutions on the ring can join to form additional rings.

In embodiments of Formula I or II, R¹¹ and R¹² are each, independently,selected from the group consisting of hydrogen, hydrocarbyls, andsubstituted hydrocarbyls, alkoxy, silyl, amino, aryloxy, halogen, andphosphino, R¹¹ and R¹² may be joined to form a saturated, substituted orunsubstituted hydrocarbyl ring, where the ring has 4, 5, 6, or 7 ringcarbon atoms and where substitutions on the ring can join to formadditional rings, or R¹¹ and R¹² may be joined to form a saturatedheterocyclic ring, or a saturated substituted heterocyclic ring wheresubstitutions on the ring can join to form additional rings.

In embodiments of Formula I or II, R¹ and R¹³ may be independentlyselected from phenyl groups that are variously substituted with betweenzero to five substituents that include F, Cl, Br, I, CF₃, NO₂, alkoxy,dialkylamino, aryl, and alkyl groups having 1 to 10 carbons, such asmethyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, and isomers thereof.

In embodiments of Formula II, preferred R¹²-E-R¹¹ groups include CH₂,CMe₂, SiMe₂, SiEt₂, SiPr₂, SiBu₂, SiPh₂, Si(aryl)₂, Si(alkyl)₂,CH(aryl), CH(Ph), CH(alkyl), and CH(2-isopropylphenyl), where alkyl is aC₁ to C₄₀ alkyl group (preferably C₁ to C₂₀ alkyl, preferably one ormore of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl,nonyl, decyl, undecyl, dodecyl, and isomers thereof), aryl is a C₅ toC₄₀ aryl group (preferably a C₆ to C₂₀ aryl group, preferably phenyl orsubstituted phenyl, preferably phenyl, 2-isopropylphenyl, or2-tertbutylphenyl).

Preferably, the R groups above and other R groups mentioned hereafter,contain from 1 to 30, preferably 2 to 20 carbon atoms, especially from 6to 20 carbon atoms.

Preferably, M is Ti, Zr, or Hf, and E is carbon, with Zr or Hf basedcomplexes being especially preferred.

In any embodiment described herein, E is carbon and R¹² and R¹¹ areindependently selected from phenyl groups that are substituted with 0,1, 2, 3, 4, or 5 substituents selected from the group consisting of F,Cl, Br, I, CF₃, NO₂, alkoxy, dialkylamino, hydrocarbyl, and substitutedhydrocarbyl groups with from one to ten carbons.

In any embodiment described herein of Formula II, R¹¹ and R¹² areindependently selected from hydrogen, methyl, ethyl, phenyl, isopropyl,isobutyl, and trimethylsilyl.

In any embodiment described herein of Formula II, R⁷, R⁸, R⁹, and R¹⁰are independently selected from hydrogen, methyl, ethyl, propyl,isopropyl, phenyl, cyclohexyl, fluoro, chloro, methoxy, ethoxy, phenoxy,and trimethylsilyl.

In any embodiment described herein of Formula I or II, R², R³, R⁴, R⁵,and R⁶ are independently selected from the group consisting of hydrogen,hydrocarbyls, alkoxy, silyl, amino, substituted hydrocarbyls, andhalogen.

In any embodiment described herein of Formula I or II, each L isindependently selected from Et₂O, MeOtBu, Et₃N, PhNMe₂, MePh₂N,tetrahydrofuran, and dimethylsulfide.

In any embodiment described herein of Formula I or II, each X isindependently selected from methyl, benzyl, trimethylsilyl, neopentyl,ethyl, propyl, butyl, phenyl, hydrido, chloro, fluoro, bromo, iodo,dimethylamido, diethylamido, dipropylamido, and diisopropylamido.

In any embodiment described herein of Formula I or II, R¹ is2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl,2,6-diisopropyl-4-methylphenyl, 2,6-diethylphenyl,2-ethyl-6-isopropylphenyl, 2,6-bis(3-pentyl)phenyl,2,6-dicyclopentylphenyl, or 2,6-dicyclohexylphenyl.

In any embodiment described herein of Formula I or II, R¹³ is phenyl,2-methylphenyl, 2-ethylphenyl, 2-propylphenyl, 2,6-dimethylphenyl,2-isopropylphenyl, 4-methylphenyl, 3,5-dimethylphenyl,3,5-di-tert-butylphenyl, 4-fluorophenyl, 3-methylphenyl,4-dimethylaminophenyl, or 2-phenylphenyl.

In any embodiment described herein of Formula II, wherein J isdihydro-1H-indenyl and R¹ is 2,6-dialkylphenyl or 2,4,6-trialkylphenyl.

In any embodiment described herein of Formula I or II, R¹ is2,6-diisopropylphenyl and R¹³ is a hydrocarbyl group containing 1, 2, 3,4, 5, 6, or 7 carbon atoms.

In another aspect of the invention there are provided various processesfor synthesizing the complexes described herein.

Ligand Synthesis

The quinolinyldiamine ligands described herein are generally prepared inmultiple steps. The main step in the synthesis of the quinolinyldiamineligand is the carbon-carbon bond coupling step shown below in Scheme 1,wherein fragment 1 and fragment 2 are joined together in a transitionmetal mediated reaction. In the specific examples described herein thecoupling step involves the use of Pd(PPh₃)₄, but other transition metalcatalysts (e.g., Ni or Cu containing complexes) are also useful for thistype of coupling reaction. In the specific examples described herein,the W* and Y* groups used were a boronic acid ester and a halide,respectively. This choice was suitable for the Pd-mediated couplingstep, but other groups may also be useful for the coupling reaction.Other possible W* and Y* groups of interest include alkali metal (e.g.,Li), alkaline earth metal halide (e.g., MgBr), zinc halide (e.g., ZnCl),zincate, halide, and triflate. In Scheme 1, R¹ through R¹³ and E are asdescribed above.

One method for the preparation of transition metal quinolinyldiamidecomplexes is by reaction of the quinolinyldiamine ligand with a metalreactant containing anionic basic leaving groups. Typical anionic basicleaving groups include dialkylamido, benzyl, phenyl, hydrido, andmethyl. In this reaction, the role of the basic leaving group is todeprotonate the quinolinyldiamine ligand. Suitable metal reactants forthis type of reaction include, but are not limited to, HfBn₄ (Bn=CH₂Ph),ZrBn₄, TiBn₄, ZrBn₂Cl₂(OEt₂), HfBn₂Cl₂(OEt₂)₂,Zr(NMe₂)₂Cl₂(dimethoxyethane), Hf(NMe₂)₂Cl₂(dimethoxyethane), Hf(NMe₂)₄,Zr(NMe₂)₄, and Hf(NEt₂)₄. In the specific examples presented hereinHf(NMe₂)₄ is reacted with a quinolinyldiamine ligand at elevatedtemperatures to form the quinolinyldiamide complex with the formation oftwo molar equivalents of dimethylamine, which is lost or removed beforethe quinolinyldiamide complex is isolated.

A second method for the preparation of transition metalquinolinyldiamide complexes is by reaction of the quinolinyldiamineligand with an alkali metal or alkaline earth metal base (e.g., BuLi,EtMgBr) to deprotonate the ligand, followed by reaction with a metalhalide (e.g., HfCl₄, ZrCl₄).

Quinolinyldiamide (QDA) metal complexes that contain metal-halide,alkoxide, or amido leaving groups may be alkylated by reaction withorganolithium, Grignard, and organoaluminum reagents as shown in Scheme2. In the alkylation reaction the alkyl groups are transferred to theQDA metal center and the leaving groups are removed. In Scheme 2, R¹through R¹³ and E are as described above and X* is a halide, alkoxide,or dialkylamido leaving group. Reagents typically used for thealkylation reaction include, but are not limited to, MeLi, MeMgBr,Me₂Mg, AlMe₃, AliBu₃, AlOct₃, and PhCH₂MgCl. Typically 2 to 20 molarequivalents of the alkylating reagent are added to the QDA complex. Thealkylations are generally performed in ethereal or hydrocarbon solventsor solvent mixtures at temperatures typically ranging from −80° C. to70° C.

In a preferred embodiment of the invention, the transition metal complexis not a metallocene. A metallocene catalyst is defined as anorganometallic compound with at least one e-bound cyclopentadienylmoiety (or substituted cyclopentadienyl moiety) and more frequently twon-bound cyclopentadienyl moieties or substituted cyclopentadienylmoieties.

Activators

The catalyst systems typically comprise a transition metal complex asdescribed above and an activator such as alumoxane or a non-coordinatinganion. Activation may be performed using alumoxane solution includingmethyl alumoxane, referred to as MAO, as well as modified MAO, referredto herein as MMAO, containing some higher alkyl groups to improve thesolubility. Particularly useful MAO can be purchased from Albemarle,typically in a 10 wt % solution in toluene. The catalyst system employedin the present invention may use an activator selected from alumoxanes,such as methyl alumoxane, modified methyl alumoxane, ethyl alumoxane,iso-butyl alumoxane, and the like.

When an alumoxane or modified alumoxane is used, thecomplex-to-activator molar ratio is from about 1:3000 to 10:1;alternatively 1:2000 to 10:1; alternatively 1:1000 to 10:1;alternatively, 1:500 to 1:1; alternatively 1:300 to 1:1; alternatively1:200 to 1:1; alternatively 1:100 to 1:1; alternatively 1:50 to 1:1;alternatively 1:10 to 1:1. When the activator is an alumoxane (modifiedor unmodified), some embodiments select the maximum amount of activatorat a 5000-fold molar excess over the catalyst precursor (per metalcatalytic site). The preferred minimum activator-to-complex ratio is 1:1molar ratio.

Activation may also be performed using non-coordinating anions, referredto as NCA's, of the type described in EP 277 003 Al and EP 277 004 Al.NCA may be added in the form of an ion pair using, for example,[DMAH]+[NCA]- in which the N,N-dimethylanilinium (DMAH) cation reactswith a basic leaving group on the transition metal complex to form atransition metal complex cation and [NCA]-. The cation in the precursormay, alternatively, be trityl. Alternatively, the transition metalcomplex may be reacted with a neutral NCA precursor, such as B(C₆F5)₃,which abstracts an anionic group from the complex to form an activatedspecies. Useful activators include N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (i.e., [PhNMe₂H]B(C₆F5)₄) andN,N-dimethylanilinium tetrakis (heptafluoronaphthyl)borate, where Ph isphenyl, and Me is methyl.

Additionally preferred activators useful herein include those describedin U.S. Pat. No. 7,247,687 at column 169, line 50 to column 174, line43, particularly column 172, line 24 to column 173, line 53.

In an embodiment of the invention described herein, the non-coordinatinganion activator is represented by the following formula (1):

(Z)_(d) ⁺(A^(d−))  (1)

wherein Z is (L-H) or a reducible Lewis acid; L is a neutral Lewis base;H is hydrogen and (L-H)⁺ is a Bronsted acid; A^(d−) is anon-coordinating anion having the charge d−; and d is an integer from 1to 3.

When Z is (L-H) such that the cation component is (L-H)d⁺, the cationcomponent may include Bronsted acids such as protonated Lewis basescapable of protonating a moiety, such as an alkyl or aryl, from thecatalyst precursor, resulting in a cationic transition metal species, orthe activating cation (L-H)d₊ is a Bronsted acid, capable of donating aproton to the catalyst precursor resulting in a transition metal cation,including ammoniums, oxoniums, phosphoniums, silyliums, and mixturesthereof, or ammoniums of methylamine, aniline, dimethylamine,diethylamine, N-methylaniline, diphenylamine, trimethylamine,triethylamine, N,N-dimethylaniline, methyldiphenylamine, pyridine,p-bromo N,N-dimethylaniline, p-nitro-N,N-dimethylaniline, phosphoniumsfrom triethylphosphine, triphenylphosphine, and diphenylphosphine,oxoniums from ethers, such as dimethyl ether diethyl ether,tetrahydrofuran, and dioxane, sulfoniums from thioethers, such asdiethyl thioethers and tetrahydrothiophene, and mixtures thereof.

When Z is a reducible Lewis acid, it may be represented by the formula:(Ar₃C⁺), where Ar is aryl or aryl substituted with a heteroatom, or a C₁to C₄₀ hydrocarbyl, the reducible Lewis acid may be represented by theformula: (Ph₃C⁺), where Ph is phenyl or phenyl substituted with aheteroatom, and/or a C₁ to C₄₀ hydrocarbyl. In an embodiment, thereducible Lewis acid is triphenyl carbenium.

Embodiments of the anion component Ad⁻ include those having the formula[Mk+Qn]d⁻ wherein k is 1, 2, or 3; n is 1, 2, 3, 4, 5, or 6, or 3, 4, 5,or 6; n-k=d; M is an element selected from Group 13 of the PeriodicTable of the Elements, or boron or aluminum, and Q is independently ahydride, bridged or unbridged dialkylamido, halide, alkoxide, aryloxide,hydrocarbyl radicals, said Q having up to 20 carbon atoms with theproviso that in not more than one occurrence is Q a halide, and two Qgroups may form a ring structure. Each Q may be a fluorinatedhydrocarbyl radical having 1 to 20 carbon atoms, or each Q is afluorinated aryl radical, or each Q is a pentafluoryl aryl radical.Examples of suitable Ad⁻ components also include diboron compounds asdisclosed in U.S. Pat. No. 5,447,895, which is fully incorporated hereinby reference.

In an embodiment in any of the NCA's represented by Formula 1 describedabove, the anion component Ad⁻ is represented by the formula[M*k*+Q*n*]d*- wherein k* is 1, 2, or 3; n* is 1, 2, 3, 4, 5, or 6 (or1, 2, 3, or 4); n*-k*=d*; M* is boron; and Q* is independently selectedfrom hydride, bridged or unbridged dialkylamido, halogen, alkoxide,aryloxide, hydrocarbyl radicals, said Q* having up to 20 carbon atomswith the proviso that in not more than 1 occurrence is Q* a halogen.

This invention also relates to a method to polymerize olefins comprisingcontacting olefins (such as propylene) with a catalyst complex asdescribed above and an NCA activator represented by the Formula (2):

R_(n)M**(ArNHaI)_(4-n)  (2)

where R is a monoanionic ligand; M** is a Group 13 metal or metalloid;ArNHaI is a halogenated, nitrogen-containing aromatic ring, polycyclicaromatic ring, or aromatic ring assembly in which two or more rings (orfused ring systems) are joined directly to one another or together; andn is 0, 1, 2, or 3. Typically the NCA comprising an anion of Formula 2also comprises a suitable cation that is essentially non-interferingwith the ionic catalyst complexes formed with the transition metalcompounds, or the cation is Z_(d) ⁺ as described above.

In an embodiment in any of the NCA's comprising an anion represented byFormula 2 described above, R is selected from the group consisting of C₁to C₃₀ hydrocarbyl radicals. In an embodiment, C₁ to C₃₀ hydrocarbylradicals may be substituted with one or more C₁ to C₂₀ hydrocarbylradicals, halide, hydrocarbyl substituted organometalloid, dialkylamido,alkoxy, aryloxy, alkysulfido, arylsulfido, alkylphosphido,arylphosphide, or other anionic substituent; fluoride; bulky alkoxides,where bulky means C₄ to C₂₀ hydrocarbyl radicals; —SRa, —NRa₂, and—PRa₂, where each Ra is independently a monovalent C₄ to C₂₀ hydrocarbylradical comprising a molecular volume greater than or equal to themolecular volume of an isopropyl substitution or a C₄ to C₂₀ hydrocarbylsubstituted organometalloid having a molecular volume greater than orequal to the molecular volume of an isopropyl substitution.

In an embodiment in any of the NCA's comprising an anion represented byFormula 2 described above, the NCA also comprises cation comprising areducible Lewis acid represented by the formula: (Ar₃C⁺), where Ar isaryl or aryl substituted with a heteroatom, and/or a C₁ to C₄₀hydrocarbyl, or the reducible Lewis acid represented by the formula:(Ph₃C⁺), where Ph is phenyl or phenyl substituted with one or moreheteroatoms, and/or C₁ to C₄₀ hydrocarbyls.

In an embodiment in any of the NCA's comprising an anion represented byFormula 2 described above, the NCA may also comprise a cationrepresented by the formula, (L-H)d⁺, wherein L is a neutral Lewis base;H is hydrogen; (L-H) is a Bronsted acid; and d is 1, 2, or 3, or (L-H)d⁺is a Bronsted acid selected from ammoniums, oxoniums, phosphoniums,silyliums, and mixtures thereof.

Further examples of useful activators include those disclosed in U.S.Pat. No. 7,297,653 and U.S. Pat. No. 7,799,879, which are fullyincorporated by reference herein.

In an embodiment, an activator useful herein comprises a salt of acationic oxidizing agent and a noncoordinating, compatible anionrepresented by the Formula (3):

(OX^(e+))_(d)(A^(d−))_(e)  (3)

wherein OX^(e+) is a cationic oxidizing agent having a charge of e+; eis 1, 2, or 3; d is 1, 2, or 3; and A^(d−) is a non-coordinating anionhaving the charge of d− (as further described above). Examples ofcationic oxidizing agents include: ferrocenium, hydrocarbyl-substitutedferrocenium, Ag⁺, or Pb⁺². Suitable embodiments of A^(d−) includetetrakis(pentafluorophenyl)borate.

Activators useful in catalyst systems herein include: trimethylammoniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-diethylaniliniumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, trimethylammoniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, and the types disclosed in U.S. Pat.No. 7,297,653, which is fully incorporated by reference herein.

Suitable activators also include: N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(perfluorophenyl)borate, [Ph₃C+][B(C₆F₅)₄—],[Me₃NH+][B(C₆F₅)₄—];1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium;and tetrakis(pentafluorophenyl)borate,4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine.

In an embodiment, the activator comprises a triaryl carbonium (such astriphenylcarbenium tetraphenylborate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate).

In an embodiment, two NCA activators may be used in the polymerizationand the molar ratio of the first NCA activator to the second NCAactivator can be any ratio. In an embodiment, the molar ratio of thefirst NCA activator to the second NCA activator is 0.01:1 to 10,000:1,or 0.1:1 to 1000:1, or 1:1 to 100:1.

In an embodiment of the invention, the NCA activator-to-catalyst ratiois a 1:1 molar ratio, or 0.1:1 to 100:1, or 0.5:1 to 200:1, or 1:1 to500:1 or 1:1 to 1000:1. In an embodiment, the NCA activator-to-catalystratio is 0.5:1 to 10:1, or 1:1 to 5:1.

In an embodiment, the catalyst compounds can be combined withcombinations of alumoxanes and NCA's (see for example, U.S. Pat. No.5,153,157; U.S. Pat. No. 5,453,410; EP 0 573 120 B1; WO 94/07928; and WO95/14044 which discuss the use of an alumoxane in combination with anionizing activator, all of which are incorporated by reference herein).

In a preferred embodiment of the invention, when an NCA (such as anionic or neutral stoichiometric activator) is used, thecomplex-to-activator molar ratio is typically from 1:10 to 1:1; 1:10 to10:1; 1:10 to 2:1; 1:10 to 3:1; 1:10 to 5:1; 1:2 to 1.2:1; 1:2 to 10:1;1:2 to 2:1; 1:2 to 3:1; 1:2 to 5:1; 1:3 to 1.2:1; 1:3 to 10:1; 1:3 to2:1; 1:3 to 3:1; 1:3 to 5:1; 1:5 to 1:1; 1:5 to 10:1; 1:5 to 2:1; 1:5 to3:1; 1:5 to 5:1; 1:1 to 1:1.2.

Alternately, a co-activator or chain transfer agent, such as a group 1,2, or 13 organometallic species (e.g., an alkyl aluminum compound suchas tri-n-octyl aluminum), may also be used in the catalyst systemherein. The complex-to-co-activator molar ratio is from 1:100 to 100:1;1:75 to 75:1; 1:50 to 50:1; 1:25 to 25:1; 1:15 to 15:1; 1:10 to 10:1;1:5 to 5:1; 1:2 to 2:1; 1:100 to 1:1; 1:75 to 1:1; 1:50 to 1:1; 1:25 to1:1; 1:15 to 1:1; 1:10 to 1:1; 1:5 to 1:1; 1:2 to 1:1; 1:10 to 2:1.

Metal Hydrocarbenyl Transfer Agents (Aluminum Vinyl Transfer Agents)

The catalyst systems described herein further comprise a metalhydrocarbenyl transfer agent (which is any group 12 or 13 metal agentthat contains at least one transferrable group that has an allyl chainend), preferably an aluminum vinyl-transfer agent, also referred to asan AVTA, (which is any aluminum agent that contains at least onetransferrable group that has an allyl chain end). An allyl chain end isrepresented by the formula H₂C═CH—CH₂—. “Allylic vinyl group,” “allylchain end,” “vinyl chain end,” “vinyl termination,” “allylic vinylgroup,” “terminal vinyl group,” and “vinyl terminated” are usedinterchangeably herein and refer to an allyl chain end. An allyl chainend is not a vinylidene chain end or a vinylene chain end. The number ofallyl chain ends, vinylidene chain ends, vinylene chain ends, and otherunsaturated chain ends is determined using ¹H NMR at 120° C. usingdeuterated tetrachloroethane as the solvent on an at least 250 MHz NMRspectrometer.

Useful transferable groups containing an allyl chain end are representedby the formula CH₂═CH—CH₂—R*, where R* represents a hydrocarbyl group ora substituted hydrocarbyl group, such as a C₁ to C₂₀ alkyl, preferablymethyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, undecyl, dodecyl, or an isomer thereof.

In the catalyst system described herein, the catalyst undergoes alkylgroup transfer with the transfer agent, which enables the formation ofpolymer chains containing one or more allyl chain ends.

Useful transferable groups containing an allyl chain end also includethose represented by the formula CH₂═CH—CH₂—R**, where R** represents ahydrocarbeneyl group or a substituted hydrocarbeneyl group, such as a C₁to C₂₀ alkylene, preferably methylene (CH₂), ethylene [(CH₂)₂],propandiyl [(CH₂)₃], butandiyl [(CH₂)₄], pentandiyl [(CH₂)₅], hexandiyl[(CH₂)₆], heptandiyl [(CH₂)₇], octandiyl [(CH₂)₈], nonandiyl [(CH₂)₉],decandiyl [(CH₂)₁₀], undecandiyl [(CH₂₀)₁₁], dodecandiyl [(CH₂)₁₂], oran isomer thereof. Useful transferable groups are preferablynon-substituted linear hydrocarbeneyl groups. Preferably, at least oneR** is a C₄-C₂₀ hydrocarbenyl group.

The term “hydrocarbeneyl” refers to a hydrocarb-di-yl divalent group,such as a C₁ to C₂₀ alkylene (i.e., methylene (CH₂), ethylene [(CH₂)₂],propandiyl [(CH₂)₃], butandiyl [(CH₂)₄], pentandiyl [(CH₂)₅], hexandiyl[(CH₂)₆], heptandiyl [(CH₂)₇], octandiyl [(CH₂)₈], nonandiyl [(CH₂)₉],decandiyl [(CH₂)₁₀], undecandiyl [(CH₂)₁₁₁], dodecandiyl [(CH₂)₁₂], andisomers thereof).

AVTA's are alkenylaluminum reagents capable of causing group exchangebetween the transition metal of the catalyst system (M^(TM)) and themetal of the AVTA (M^(AVTA)). The reverse reaction may also occur suchthat the polymeryl chain is transferred back to the transition metal ofthe catalyst system. This reaction scheme is illustrated below:

wherein M^(TM) is an active transition metal catalyst site and P is thepolymeryl chain, M^(AVTA) is the metal of the AVTA, and R is atransferable group containing an allyl chain end, such as a hydrocarbylgroup containing an allyl chain end, also called a hydrocarbenyl oralkenyl group.

Catalyst systems of this invention preferably have high rates of olefinpropagation and negligible or no chain termination via beta hydrideelimination, beta methyl elimination, or chain transfer to monomerrelative to the rate of chain transfer to the AVTA or other chaintransfer agent, such as an aluminum alkyl, if present. Quinolinyldiamidocatalyst complexes (see U.S. Ser. No. 62/357,033, filed Jun. 30, 2016)and/or other catalyst compounds (U.S. Pat. No. 7,973,116; U.S. Pat. No.8,394,902; U.S. Pat. No. 8,674,040; U.S. Pat. No. 8,710,163; U.S. Pat.No. 9,102,773; US 2014/0256893; US 2014/0316089; and US 2015/0141601)activated with non-coordinating activators such as dimethylaniliniumtetrakis(perfluorophenyl)borate and/or dimethylaniliniumtetrakis(perfluoronaphthyl)borate are particularly useful in thecatalyst systems of this invention. Compound 3, described above isparticularly preferred.

In any embodiment of the invention described herein, the catalyst systemcomprises an aluminum vinyl transfer agent, which is typicallyrepresented by the formula (A):

Al(R′)_(3-v)(R)_(v)

where R is a hydrocarbenyl group containing 4 to 20 carbon atoms havingan allyl chain end, R′ is a hydrocarbyl group containing 1 to 30 carbonatoms, and v is 0.1 to 3, alternately 1 to 3, alternately 1.1 to lessthan 3, alternately v is 0.5 to 2.9, 1.1 to 2.9, alternately 1.5 to 2.7,alternately 1.5 to 2.5, alternately 1.8 to 2.2. The compoundsrepresented by the formula Al(R′)_(3-v)(R)_(v) are typically a neutralspecies, but anionic formulations may be envisioned, such as thoserepresented by formula (B): [Al(R′)_(4-w)(R)_(w)]⁻, where w is 0.1 to 4,R is a hydrocarbenyl group containing 4 to 20 carbon atoms having anallyl chain end, and R′ is a hydrocarbyl group containing 1 to 30 carbonatoms.

In any embodiment of any formula for a metal hydrocarbenyl transferagent, such as formula A or B, described herein, each R′ isindependently chosen from C₁ to C₃₀ hydrocarbyl groups (such as a C₁ toC₂₀ alkyl groups, preferably methyl, ethyl, propyl, butyl, pentyl,hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, or an isomerthereof), and R is represented by the formula:

—(CH₂)_(n)CH═CH₂

where n is an integer from 2 to 18, preferably 6 to 18, preferably 6 to12, preferably 6.

In any embodiment of the invention described herein, particularly usefulAVTAs include, but are not limited to, tri(but-3-en-1-yl)aluminum,tri(pent-4-en-1-yl)aluminum, tri(oct-7-en-1-yl)aluminum,tri(non-8-en-1-yl)aluminum, tri(dec-9-en-1-yl)aluminum,dimethyl(oct-7-en-1-yl)aluminum, diethyl(oct-7-en-1-yl)aluminum,dibutyl(oct-7-en-1-yl)aluminum, diisobutyl(oct-7-en-1-yl)aluminum,diisobutyl(non-8-en-1-yl)aluminum, diisobutyl(dec-9-en-1-yl)aluminum,diisobutyl(dodec-11-en-1-yl)aluminum, and the like. Mixtures of one ormore AVTAs may also be used. In some embodiments of the invention,isobutyl-di(oct-7-en-1-yl)-aluminum,isobutyl-di(dec-9-en-1-yl)-aluminum,isobutyl-di(non-8-en-1-yl)-aluminum,isobutyl-di(hept-6-en-1-yl)-aluminum are preferred.

Particularly useful metal hydrocarbenyl transfer agents comprises one ormore of tri(but-3-en-1-yl)aluminum, tri(pent-4-en-1-yl)aluminum,tri(oct-7-en-1-yl)aluminum, tri(non-8-en-1-yl)aluminum,tri(dec-9-en-1-yl)aluminum, dimethyl(oct-7-en-1-yl)aluminum,diethyl(oct-7-en-1-yl)aluminum, dibutyl(oct-7-en-1-yl)aluminum,diisobutyl(oct-7-en-1-yl)aluminum, diisobutyl(non-8-en-1-yl)aluminum,dimethyl(dec-9-en-1-yl)aluminum, diethyl(dec-9-en-1-yl)aluminum,dibutyl(dec-9-en-1-yl)aluminum, diisobutyl(dec-9-en-1-yl)aluminum, anddiisobutyl(dodec-11-en-1-yl)aluminum.

Useful aluminum vinyl transfer agents include organoaluminum compoundreaction products between aluminum reagent (AlR^(a3)) and an alkyldiene. Suitable alkyl dienes include those that have two “alphaolefins”, as described above, at two termini of the carbon chain. Thealkyl diene can be a straight chain or branched alkyl chain andsubstituted or unsubstituted. Exemplary alkyl dienes include but are notlimited to, for example, 1,3-butadiene, 1,4-pentadiene, 1,6-heptadiene,1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene,1,11-dodecadiene, 1,12-tridecadiene, 1,13-tetradecadiene,1,14-pentadecadiene, 1,15-hexadecadiene, 1,16-heptadecadiene,1,17-octadecadiene, 1,18-nonadecadiene, 1,19-eicosadiene,1,20-heneicosadiene, etc. Exemplary aluminum reagents includetriisobutylaluminum, diisobutylaluminumhydride,isobutylaluminumdihydride and aluminum hydride (AlH₃).

In any embodiment of the invention described herein, R″ is butenyl,pentenyl, heptenyl, octenyl or decenyl. In some embodiments R″ ispreferably octenyl or decenyl.

In any embodiment of the invention described herein, R′ is methyl,ethyl, propyl, isobutyl, or butyl. In any embodiment of the inventiondescribed herein, R′ is isobutyl.

In any embodiment of the invention described herein, v is about 2, or vis 2.

In any embodiment of the invention described herein, v is about 1, or vis 1, preferably from about 1 to about 2.

In any embodiment of the invention described herein, v is an integer ora non-integer, preferably v is from 1.1 to 2.9, from about 1.5 to about2.7, e.g., from about 1.6 to about 2.4, from about 1.7 to about 2.4,from about 1.8 to about 2.2, from about 1.9 to about 2.1 and all rangesthere between.

In preferred embodiments of the invention described herein, R′ isisobutyl and each R″ is octenyl or decenyl, preferably R′ is isobutyl,each R″ is octenyl or decenyl, and v is from 1.1 to 2.9, from about 1.5to about 2.7, e.g., from about 1.6 to about 2.4, from about 1.7 to about2.4, from about 1.8 to about 2.2, from about 1.9 to about 2.1.

The amount of v (the aluminum alkenyl) is described using the formulas:(3-v)+v=3, and Al(R′)_(3-v)(R″)_(v) where R″ is a hydrocarbenyl groupcontaining 4 to 20 carbon atoms having an allyl chain end, R′ is ahydrocarbyl group containing 1 to 30 carbon atoms, and v is 0.1 to 3(preferably 1.1 to 3). This formulation represents the observed averageof organoaluminum species (as determined by ¹H NMR) present in amixture, which may include any of Al(R′)₃, Al(R′)₂(R″), Al(R′)(R″)₂, andAl(R″)₃. ¹H NMR spectroscopic studies are performed at room temperatureusing a Bruker 400 MHz NMR. Data is collected using samples prepared bydissolving 10-20 mg the compound in 1 mL of C₆D₆. Samples are thenloaded into 5 mm NMR tubes for data collection. Data is recorded using amaximum pulse width of 45°, 8 seconds between pulses and signalaveraging either 8 or 16 transients. The spectra are normalized toprotonated tetrachloroethane in the C₆D₆. The chemical shifts (6) arereported as relative to the residual protium in the deuterated solventat 7.15 ppm.

In still another aspect, the aluminum vinyl-transfer agent has less than50 wt % dimer present, based upon the weight of the AVTA, preferablyless than 40 wt %, preferably less than 30 wt %, preferably less than 20wt %, preferably less than 15 wt %, preferably less than 10 wt %,preferably less than 5 wt %, preferably less than 2 wt %, preferablyless than 1 wt %, preferably 0 wt % dimer. Alternately dimer is presentat from 0.1 to 50 wt %, alternately 1 to 20 wt %, alternately at from 2to 10 wt %. Dimer is the dimeric product of the alkyl diene used in thepreparation of the AVTA. The dimer can be formed under certain reactionconditions, and is formed from the insertion of a molecule of diene intothe Al—R bond of the AVTA, followed by beta-hydride elimination. Forexample, if the alkyl diene used is 1,7-octadiene, the dimer is7-methylenepentadeca-1,14-diene. Similarly, if the alkyl diene is1,9-decadiene, the dimer is 9-methylenenonadeca-1,18-diene.

Useful compounds can be prepared by combining an aluminum reagent (suchas alkyl aluminum) having at least one secondary alkyl moiety (such astriisobutylaluminum) and/or at least one hydride, such as adialkylaluminum hydride, a monoalkylaluminum dihydride or aluminumtrihydride (aluminum hydride, AlH₃) with an alkyl diene and heating to atemperature that causes release of an alkylene byproduct. The use ofsolvent(s) is not required. However, non-polar solvents can be employed,such as, as hexane, pentane, toluene, benzene, xylenes, and the like, orcombinations thereof.

In an embodiment of the invention, the AVTA is free of coordinatingpolar solvents such as tetrahydrofuran and diethylether.

After the reaction is complete, solvent if, present can be removed andthe product can be used directly without further purification.

The AVTA to catalyst complex equivalence ratio can be from about 1:100to 500,000:1. More preferably, the molar ratio of AVTA to catalystcomplex is greater than 5, alternately greater than 10, alternatelygreater than 15, alternately greater than 20, alternately greater than25, alternately greater than 30.

In another embodiment of the invention, the metal hydrocarbenyl transferagent is an alumoxane formed from the hydrolysis of the AVTA.Alternatively, the alumoxane can be formed from the hydrolysis of theAVTA in combination with other aluminum alkyl(s). The alumoxanecomponent is an oligomeric compound which is not well characterized, butcan be represented by the general formula (R—Al—O)_(m) which is a cycliccompound, or may be R′(R—Al—O)_(m)—AlR′₂ which is a linear compoundwhere R′ is as defined above and at least one R′ is the same as R (asdefined above), and m is from about 4 to 25, with a range of 13 to 25being preferred. Most preferably all R′ are R. An alumoxane is generallya mixture of both the linear and cyclic compounds.

Supports

The complexes described herein may be supported (with or without anactivator and with or without a transfer agent) by any method effectiveto support other coordination catalyst systems, effectively meaning thatthe catalyst so prepared can be used for polymerizing olefin(s) in aheterogeneous process. The catalyst precursor, activator, optionaltransfer agent, co-activator if needed, suitable solvent, and supportmay be added in any order or simultaneously. Typically, the complex,activator, and optional transfer agent may be combined in solvent toform a solution. Then the support is added, and the mixture is stirredfor 1 minute to 10 hours. The total solution volume may be greater thanthe pore volume of the support, but some embodiments limit the totalsolution volume below that needed to form a gel or slurry (about 90% to400%, preferably about 100% to 200% of the pore volume). After stirring,the residual solvent is removed under vacuum, typically at ambienttemperature and over 10-16 hours. But greater or lesser times andtemperatures are possible.

The complex may also be supported absent the activator, and in thatcase, the activator (and co-activator if needed) is added to apolymerization process' liquid phase. Additionally, two or moredifferent complexes may be placed on the same support. Likewise, two ormore activators or an activator and co-activator may be placed on thesame support. Likewise the transfer agent may be added to thepolymerization reaction separately from the supported catalyst complexand/or activator.

Suitable solid particle supports are typically comprised of polymeric orrefractory oxide materials, each being preferably porous. Preferably,any support material that has an average particle size greater than 10μm is suitable for use in this invention. Various embodiments select aporous support material, such as for example, talc, inorganic oxides,inorganic chlorides, for example magnesium chloride and resinous supportmaterials such as polystyrene polyolefin or polymeric compounds or anyother organic support material and the like. Some embodiments selectinorganic oxide materials as the support material including Group-2, -3,-4, -5, -13, or -14 metal or metalloid oxides. Some embodiments selectthe catalyst support materials to include silica, alumina,silica-alumina, and their mixtures. Other inorganic oxides may serveeither alone or in combination with the silica, alumina, orsilica-alumina. These are magnesia, titania, zirconia, and the like. Thesupport can optionally double as the activator component; however, anadditional activator may also be used.

The support material may be pre-treated by any number of methods. Forexample, inorganic oxides may be calcined, chemically treated withdehydroxylating agents such as aluminum alkyls and the like, or both.

As stated above, polymeric carriers will also be suitable in accordancewith the invention, see, for example, the descriptions in WO 95/15815and U.S. Pat. No. 5,427,991. The methods disclosed may be used with thecatalyst complexes, activators or catalyst systems of this invention toadsorb or absorb them on the polymeric supports, particularly if made upof porous particles, or may be chemically bound through functionalgroups bound to or in the polymer chains.

Useful supports typically have a surface area of from 10-700 m²/g, apore volume of 0.1-4.0 cc/g and an average particle size of 10-500 μm.Some embodiments select a surface area of 50-500 m2/g, a pore volume of0.5-3.5 cc/g, or an average particle size of 20-200 am. Otherembodiments select a surface area of 100-400 m2/g, a pore volume of0.8-3.0 cc/g, and an average particle size of 30-100 μm. Useful supportstypically have a pore size of 10-1000 Angstroms, alternatively 50-500Angstroms, or 75-350 Angstroms.

The catalyst complexes described herein are generally deposited on thesupport at a loading level of 10-100 micromoles of complex per gram ofsolid support; alternately 20-80 micromoles of complex per gram of solidsupport; or 40-60 micromoles of complex per gram of support. But greateror lesser values may be used provided that the total amount of solidcomplex does not exceed the support's pore volume.

Polymerization

Invention catalyst complexes are useful in polymerizing unsaturatedmonomers conventionally known to undergo coordination-catalyzedpolymerization such as solution, slurry, gas-phase, and high-pressurepolymerization. Typically, one or more of the complexes describedherein, one or more activators, one or more transfer agents (such as analuminum vinyl transfer agent) and one or more monomers are contacted toproduce polymer. The complexes may be supported and, as such, will beparticularly useful in the known, fixed-bed, moving-bed, fluid-bed,slurry, gas phase, solution, or bulk operating modes conducted insingle, series, or parallel reactors.

One or more reactors in series or in parallel may be used in the presentinvention.

The complexes, activator, transfer agent, and, when required,co-activator, may be delivered as a solution or slurry, eitherseparately to the reactor, activated in-line just prior to the reactor,or pre-activated and pumped as an activated solution or slurry to thereactor. Polymerizations are carried out in either single reactoroperation, in which monomer, comonomers,catalyst/activator/co-activator, optional scavenger, and optionalmodifiers are added continuously to a single reactor or in seriesreactor operation, in which the above components are added to each oftwo or more reactors connected in series. The catalyst components can beadded to the first reactor in the series. The catalyst component mayalso be added to both reactors, with one component being added to thefirst reaction and another component to other reactors. In one preferredembodiment, the complex is activated in the reactor in the presence ofolefin and transfer agent.

In a particularly preferred embodiment, the polymerization process is acontinuous process.

Polymerization process used herein typically comprises contacting one ormore alkene monomers with the complexes, activators and transfer agentsdescribed herein. For purpose of this invention alkenes are defined toinclude multi-alkenes (such as dialkenes) and alkenes having just onedouble bond. Polymerization may be homogeneous (solution or bulkpolymerization) or heterogeneous (slurry—in a liquid diluent, or gasphase—in a gaseous diluent). In the case of heterogeneous slurry or gasphase polymerization, the complex and activator may be supported. Silicais useful as a support herein. Chain transfer agents (such as hydrogenor trialkylaluminums) may be used in the practice of this invention.

The present polymerization processes may be conducted under conditionspreferably including a temperature of about 30° C. to about 200° C.,preferably from 60° C. to 195° C., preferably from 75° C. to 190° C. Theprocess may be conducted at a pressure of from 0.05 to 1500 MPa. In apreferred embodiment, the pressure is between 1.7 MPa and 30 MPa, or inanother embodiment, especially under supercritical conditions, thepressure is between 15 MPa and 1500 MPa.

If branching (such as a g′vis of less than 0.90) is desired in thepolymer product, then, among other things, one may increase theconcentration of the metal hydrocarbenyl transfer agent, increase thetemperature of the polymerization reaction, increase the solids contentin the polymerization reaction mass (i.e., increase the solids content)or increase the residence time of the polymerization. Likewise if a morelinear polymer is desired, then then, among other things, one may reducethe concentration of the metal hydrocarbenyl transfer agent, reduce thetemperature of the polymerization reaction, reduce the solids content inthe polymerization reaction mass (i.e., increase the solids content) orreduce the residence time of the polymerization.

Monomers

Monomers useful herein include olefins having from 2 to 40 carbon atoms,alternately 2 to 12 carbon atoms (preferably ethylene, propylene,butylene, pentene, hexene, heptene, octene, nonene, decene, anddodecene) and, optionally, also polyenes (such as dienes). Particularlypreferred monomers include ethylene, and mixtures of C₂ to C₁₀ alphaolefins, such as ethylene-propylene, ethylene-hexene, ethylene-octene,propylene-hexene, and the like.

The catalyst systems described herein are also particularly effectivefor the polymerization of ethylene, either alone or in combination withat least one other olefinically unsaturated monomer, such as a C₃ to C₂₀α-olefin, and particularly a C₃ to C₁₂ α-olefin. Likewise, the presentcomplexes are also particularly effective for the polymerization ofpropylene, either alone or in combination with at least one otherolefinically unsaturated monomer, such as ethylene or a C₄ to C₂₀α-olefin, and particularly a C₄ to C₂₀ α-olefin.

The catalyst systems described herein are also particularly effectivefor the polymerization of ethylene and propylene, either alone or incombination with at least one other olefinically unsaturated monomer,such as a C₄ to C₂₀ diene, and particularly a C₃ to C₁₂ diene.

Examples of preferred α-olefins include ethylene, propylene, butene-1,pentene-1, hexene-1, heptene-1, octene-1, nonene-1, decene-1,dodecene-1, 4-methylpentene-1, 3-methylpentene-1, 3, 5,5-trimethylhexene-1, and 5-ethylnonene-1.

In some embodiments, the monomer mixture comprises one or more dienes atup to 10 wt %, such as from 0.00001 to 1.0 wt %, for example from 0.002to 0.5 wt %, such as from 0.003 to 0.2 wt %, based upon the monomermixture. Non-limiting examples of useful dienes include,cyclopentadiene, norbornadiene, dicyclopentadiene,5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 1,4-hexadiene,1,5-hexadiene, 1,5-heptadiene, 1,6-heptadiene, 6-methyl-1,6-heptadiene,1,7-octadiene, 7-methyl-1,7-octadiene, 1,9-decadiene, and9-methyl-1,9-decadiene.

Where olefins are used that give rise to short chain branching, such aspropylene, the catalyst systems may, under appropriate conditions,generate stereoregular polymers or polymers having stereoregularsequences in the polymer chains.

In a preferred embodiment, the catalyst systems described herein areused in any polymerization process described above to produce ethylenehomopolymers or copolymers, propylene homopolymers or copolymers,particularly ethylene-propylene copolymers and copolymers andethylene-propylene-diene monomer copolymers.

Scavengers

In some embodiments, when using the complexes described herein,particularly when they are immobilized on a support, the catalyst systemwill additionally comprise one or more scavenging compounds. Here, theterm scavenging compound means a compound that removes polar impuritiesfrom the reaction environment. These impurities adversely affectcatalyst activity and stability. Typically, the scavenging compound willbe an organometallic compound such as the Group-13 organometalliccompounds of U.S. Pat. No. 5,153,157; U.S. Pat. No. 5,241,025; WO1991/09882; WO 1994/03506; WO 1993/14132; and that of WO 1995/07941.Exemplary compounds include triethyl aluminum, triethyl borane,tri-iso-butyl aluminum, methyl alumoxane, iso-butyl alumoxane,tri-n-octyl aluminum, bis(diisobutylaluminum)oxide, modifiedmethylalumoxane. (Useful modified methylalumoxane include cocatalysttype 3A (commercially available from Akzo Chemicals, Inc. under thetrade name Modified Methylalumoxane type 3A) and those described in U.S.Pat. No. 5,041,584). Those scavenging compounds having bulky or C₆-C₂₀linear hydrocarbyl substituents connected to the metal or metalloidcenter usually minimize adverse interaction with the active catalyst.Examples include triethylaluminum, but more preferably, bulky compoundssuch as tri-iso-butyl aluminum, tri-iso-prenyl aluminum, and long-chainlinear alkyl-substituted aluminum compounds, such as tri-n-hexylaluminum, tri-n-octyl aluminum, or tri-n-dodecyl aluminum. Whenalumoxane is used as the activator, any excess over that needed foractivation will scavenge impurities and additional scavenging compoundsmay be unnecessary. Alumoxanes also may be added in scavengingquantities with other activators, e.g., methylalumoxane,[Me₂HNPh]⁺[B(pfp)₄]- or B(pfp)₃ (perfluorophenyl=pfp=C₆F₅).

In embodiments, the transfer agent, such as the aluminum vinyl transferagent, may also function as a scavenger.

In a preferred embodiment, two or more catalyst complexes as describedherein are combined with a chain transfer agent, suchtri-n-octylaluminum, in the same reactor with monomer. Alternately, oneor more complexes are combined with another catalyst (such as ametallocene) and a chain transfer agent, such as tri-n-octylaluminum, inthe same reactor with monomer.

Polymer Products

While the molecular weight of the polymers produced herein is influencedby reactor conditions including temperature, monomer concentration andpressure, the presence of chain terminating agents and the like, thehomopolymer and copolymer products produced by the present process mayhave an Mw of about 1,000 to about 2,000,000 g/mol, alternately of about30,000 to about 600,000 g/mol, or alternately of about 100,000 to about500,000 g/mol, as determined by Gel Permeation Chromatography. Preferredpolymers produced herein may be homopolymers or copolymers. In apreferred embodiment, the comonomer(s) are present at up to 50 mol %,preferably from 0.01 to 40 mol %, preferably 1 to 30 mol %, preferablyfrom 5 to 20 mol %.

The polymers produced by the process of the invention can be used in awide variety of products and end-use applications. The polymers producedcan be homo- and co-polymers of ethylene and propylene and includelinear low density polyethylene, elastomers, plastomers, high-densitypolyethylenes, medium density polyethylenes, low density polyethylenes,polypropylene and polypropylene copolymers. Polymers, typically ethylenebased copolymers, have a density of from 0.86 g/cc to 0.97 g/cc; densitybeing measured in accordance with ASTM-D-1238. Propylene based polymersproduced include isotactic polypropylene, atactic polypropylene andrandom, or impact copolymers.

The polymers of embodiments of the invention may have an M_(n)(number-average molecular weight) value from 300 to 1,000,000, orbetween from 700 to 300,000 g/mol. For low weight molecular weightapplications, such as those copolymers useful in lubricating and fueloil compositions, an M_(n) of 300 to 20,000 is contemplated, or lessthan or equal to 10,000 g/mol. Additionally, copolymer of embodiments ofthe invention will comprise a molecular weight distribution(M_(w)/M_(n)) in the range of >1, or >1.5 or <6, or <4 or <3, preferablyfrom greater than 1 to 40, alternatively from 1.5 to 20, alternativelyfrom 1.5 to 10, alternatively from 1.6 to 6, alternatively from 1.5 to4, or alternatively from 2 to 3.

Preferred propylene polymer, preferably homopolymer, produced herein hasan M_(w) of 20,000 up to 2,000,000 g/mol.

For higher molecular weight applications, preferred polymer, preferablyhomopolymer, produced herein has an M_(w) of 20,000 up to 2,000,000g/mol, alternately 50,000 to 1,500,000 g/mol, alternately 100,000 to1,300,000 g/mol, alternately 300,000 to 1,300,000 g/mol, alternately500,000 to 1,300,000 g/mol.

For higher molecular weight applications, preferred polymer, preferablyhomopolymer, produced herein has an M_(w) of 20,000 up to 2,000,000g/mol and a g′vis of more than 0.5, alternately 0.90 or more,alternately 0.95 or more, alternately 0.98 or more.

For lower molecular weight applications, preferred polymer, preferablyhomopolymer, produced herein has an M_(w) of less than 100,000 g/mol anda g′vis of 0.90 or less, alternately 0.85 or less, alternately 0.80 orless, alternately 0.75 or less, alternately 0.70 or less, alternately0.60 or less.

End Uses

The polymers of this invention may be blended and/or coextruded with anyother polymer. Non-limiting examples of other polymers include linearlow density polyethylenes, elastomers, plastomers, high pressure lowdensity polyethylene, high density polyethylenes, isotacticpolypropylene, ethylene propylene copolymers and the like.

Articles made using polymers produced herein may include, for example,molded articles (such as containers and bottles, e.g., householdcontainers, industrial chemical containers, personal care bottles,medical containers, fuel tanks, and storageware, toys, sheets, pipes,tubing) films, non-wovens, and the like. It should be appreciated thatthe list of applications above is merely exemplary, and is not intendedto be limiting.

In particular, polymers produced by the process of the invention andblends thereof are useful in such forming operations as film, sheet, andfiber extrusion and co-extrusion as well as blow molding, injectionmolding, roto-molding. Films include blown or cast films formed bycoextrusion or by lamination useful as shrink film, cling film, stretchfilm, sealing film or oriented films.

EXPERIMENTAL

All manipulations were performed under an inert atmosphere using glovebox techniques unless otherwise stated. Benzene-d₆ (Cambridge Isotopesor Sigma Aldrich) was degassed and dried over 3A molecular sieves priorto use. CDCl₃ (Deutero GmbH) was used as received.

Diisobutylaluminum hydride (DIBAL-H) was purchased from Akzo NobelSurface Chemistry LLC and used as received. Triisobutyl aluminum (TIBAL)was purchased from Akzo Nobel and was used as received. 1,7-octadienewere purchased from Sigma Aldrich and purified by the followingprocedure prior to use. The diene was purged under nitrogen for 30minutes and then this was stored over 3A molecular sieves for overnight.Further this was stirred with NaK (sodium-potassium alloy) for overnightand then filtered through basic alumina column prior to use.1,9-decadiene was purified by prior to use.

Preparation of Isobutyldi(oct-7-en-1-yl)aluminum, ^(i)BuAl(Oct=)₂(AVTA1)

A neat 1,7-octadiene (34.85 g, 316 mmol) was added to DIBAL-H (3.980 g,28.0 mmol) at room temperature. The resulting mixture was stirred underreflux at 110° C. for 60 minutes and then continuously stirred at 70° C.overnight. The excess 1,7-octadiene from the reaction mixture wasremoved in vacuo to obtain a colorless viscous oil of AVTA1 (8.10 g,97%). The product formation was confirmed by ¹H NMR and based on therelative integration the molecular formula of was assigned as(C₄H₉)_(1.17)Al(CsH₁₅)_(1.83). ¹H NMR (400 MHz, benzene-d₆): δ=5.81 (m,2H, ═CH), 5.05 (m, 4H, ═CH₂), 2.03 (m, 8H, —CH₂), 1.59 (m, 1H, iBu-CH),1.38 (m, 12H, —CH₂), 1.09 (d, 6H, iBu-CH₃), 0.51 (t, 4H, Al—CH₂), 0.31(d, 2H, iBu-CH₂) ppm.

Preparation of Isobutyldi(oct-7-en-1-yl)aluminum, ^(i)BuAl(Oct=)₂(AVTA2)

1,7-Octadiene (250 mL, 1.69 mol) was loaded into a round-bottomed flask.Diisobutylaluminum hydride (27.4 mL, 0.153 mol) was added dropwise over20 minutes. The mixture was then placed into a metal block maintained at117° C. After about 20 minutes the solution reached 107° C. andmaintained this temperature. Gas evolution was observed at this time.After 125 minutes the mixture was cooled to ambient temperature and thevolatiles were removed to afford a nearly colorless oil. The oil wasplaced under reduced pressure (ca. 60 mTorr) and warmed to 50° C. for 30minutes to remove any trace 1,7-octadiene. H-NMR spectroscopic dataindicated that the product had the average formula ofAl(i-Bu)_(0.86)(octenyl)_(2.14) with an additional 0.2 molar equivalentof what is presumed to be the triene formed by the insertion of1,7-octadiene into an Al-octenyl bond followed by beta hydrideelimination. Yield: 54.0 g.

Preparation of Isobutyldi(dec-9-en-1-yl)aluminum, ^(i)BuAl(Dec=)₂(AVTA3)

1,9-Decadiene (500 mL, 2.71 mol) was loaded into a round bottomed flask.Diisobutylaluminum hydride (30.2 mL, 0.170 mol) was added dropwise over15 minutes. The mixture was then placed in a metal block maintained at110° C. After 30 minutes the solution had stabilized at a temperature of104+C. The mixture was kept at this temperature for an additional 135minutes at which time H-NMR spectroscopic data indicated that thereaction had progressed to the desired amount. Cooled to ambienttemperature. The excess 1,9-decadiene was removed by vacuum distillationat 44° C./120 mTorr over a 2.5 hours. The product was further distilledat 50° C./120 mTorr for an additional hour to ensure complete removal ofall 1,9-decadiene. The isolated product was a clear colorless oil. HNMRspectroscopic data suggests an average formulation ofAl(i-Bu)_(0.9)(decenyl)_(2.1) with an additional ca. 0.2 molarequivalent of what is presumed to be the triene formed by the insertionof 1,9-decadiene into an Al-decenyl bond followed by beta hydrideelimination. Yield: 70.9 g.

Catalyst Complexes

Complex A was prepared as described in 62/357,033, filed Jun. 30, 2016.Complex B was prepared as follows:

8-(2,6-Diisopropylphenylamino)quinolin-2(1H)-one

To a suspension of NaH (5.63 g of 60 wt % in mineral oil, 140 mmol) intetrahydrofuran (1000 mL) was added 8-bromoquinolin-2(1H)-one (30.0 g,134 mmol) in small portions at 0° C. The obtained reaction mixture waswarmed to room temperature, stirred for 30 min, and then cooled to 0° C.Then t-butyldimethylsilylchloride (20.2 g, 134 mmol) was added in oneportion. This mixture was stirred for 30 min at room temperature andthen poured into water (1 L). The protected 8-bromoquinolin-2(1H)-onewas extracted with diethyl ether (3×400 mL). The combined extracts weredried over Na₂SO₄ and then evaporated to dryness. Yield 45.2 g (quant.,99% purity by GC/MS) of a dark red oil. To a solution of2,6-diisopropylaniline (27.7 mL, 147 mmol) and toluene (1.5 L) was addedn-butyllithium (60.5 mL, 147 mmol, 2.5 M in hexanes) at roomtemperature. The obtained suspension was heated briefly to 100° C. andthen cooled to room temperature. To the reaction mixture was addedPd₂(dba)₃ (dba=dibenzylideneacetone) (2.45 g, 2.68 mmol) and XPhos(XPhos=2-Dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl) (2.55 g,5.36 mmol) followed by the addition of the protected8-bromoquinolin-2(1H)-one (45.2 g, 134 mmol). The obtained dark brownsuspension was heated at 60° C. until lithium salt precipitatedisappeared (ca. 30 min). The resulting dark red solution was quenchedby addition of water (100 mL), and the organic layer was separated,dried over Na₂SO₄ and then evaporated to dryness. The obtained oil wasdissolved in a mixture of dichloromethane (1000 mL) and methanol (500mL), followed by an addition of 12 M HCl (50 mL). The reaction mixturewas stirred at room temperature for 3 h, then poured into 5% K₂CO₃ (2L). The product was extracted with dichloromethane (3×700 mL). Thecombined extracts were dried over Na₂SO₄, filtered, and then evaporatedto dryness. The resulting solid was triturated with n-hexane (300 mL),and the obtained suspension collected on a glass frit. The precipitatewas dried in vacuum. Yield 29.0 g (67%) of a marsh-green solid. Anal.calc. for C₂₁H₂₄N₂O: C, 78.71; H, 7.55; N, 8.74. Found: C, 79.00; H,7.78; N, 8.50. ¹H NMR (CDCl₃): δ 13.29 (br.s, 1H), 7.80-7.81 (d, 1H,J=9.5 Hz), 7.35-7.38 (m, 1H), 7.29-7.30 (m, 3H), 6.91-6.95 (m, 2H),6.58-6.60 (d, 1H, J=9.5 Hz), 6.27-6.29 (m, 1H), 3.21 (sept, 2H, J=6.9Hz), 1.25-1.26 (d, 6H, J=6.9 Hz), 1.11-1.12 (d, 6H, J=6.9 Hz).

2-Chloro-N-(2,6-diisopropylphenyl)quinolin-8-amine

29.0 g (90.6 mmol) of 8-(2,6-diisopropylphenylamino)quinolin-2(1H)-onewas added to 400 mL of POCl₃ in one portion. The resulting suspensionwas heated for 40 h at 105° C., then cooled to room temperature, andpoured into 4000 cm³ of a crushed ice. The crude product was extractedwith 3×400 mL of diethyl ether. The combined extract was dried overK₂CO₃ and then evaporated to dryness. The resulting solid was trituratedwith 30 mL of cold n-hexane, and the formed suspension was collected ona glass frit. The obtained solid was dried in vacuum. Yield 29.0 g (95%)of a yellow-green solid. Anal. calc. for C₂₁H₂₃N₂Cl: C, 74.43; H, 6.84;N, 8.27. Found: C, 74.68; H, 7.02; N, 7.99. ¹H NMR (CDCl₃): δ 8.04-8.05(d, 1H, J=8.6 Hz), 7.38-7.39 (d, 1H, J=8.5 Hz), 7.33-7.36 (m, 1H),7.22-7.27 (m, 4H), 7.04-7.06 (d, 1H, J=8.1 Hz), 6.27-6.29 (d, 1H, J=7.8Hz), 3.20 (sept, 2H, J=6.9 Hz), 1.19-1.20 (d, 6H, J=6.9 Hz), 1.10-1.11(d, 6H, J=6.9 Hz).

8-Bromo-1,2,3,4-tetrahydronaphthalen-1-ol

To a mixture of 78.5 g (530 mmol) of 1,2,3,4-tetrahydronaphthalen-1-ol,160 mL (1.06 mol) of TMEDA, and 3000 mL of pentane cooled to −20° C. 435mL (1.09 mol) of 2.5 M ^(n)BuLi in hexanes was added dropwise. Theobtained mixture was refluxed for 12 h, then cooled to −80° C., and 160mL (1.33 mol) of 1,2-dibromotetrafluoroethane was added. The obtainedmixture was allowed to warm to room temperature and then stirred for 12h at this temperature. After that, 100 mL of water was added. Theresulting mixture was diluted with 2000 mL of water, and the organiclayer was separated. The aqueous layer was extracted with 3×400 mL oftoluene. The combined organic extract was dried over Na₂SO₄ and thenevaporated to dryness. The residue was distilled using the Kugelrohrapparatus, b.p. 150-160° C./1 mbar. The obtained yellow oil wasdissolved in 100 mL of triethylamine, and the formed solution was addeddropwise to a stirred solution of 71.0 mL (750 mmol) of acetic anhydrideand 3.00 g (25.0 mmol) of DMAP in 105 mL of triethylamine. The formedmixture was stirred for 5 min, then 1000 mL of water was added, and theobtained mixture was stirred for 12 h. After that, the reaction mixturewas extracted with 3×200 mL of ethyl acetate. The combined organicextract was washed with aqueous Na₂CO₃, dried over Na₂SO₄, and thenevaporated to dryness. The residue was purified by flash chromatographyon silica gel 60 (40-63 um, eluent: hexane-ethyl acetate=30:1, vol.).The isolated ester was dissolved in 1500 mL of methanol, 81.0 g (1.45mol) of KOH was added, and the obtained mixture was heated to reflux for3 h. The reaction mixture was then cooled to room temperature and pouredinto 4000 mL of water. The title product was extracted with 3×300 mL ofdichloromethane. The combined organic extract was dried over Na₂SO₄ andthen evaporated to dryness. Yield 56.0 g (47%) of a white crystallinesolid. ¹H NMR (CDCl₃): δ 7.38-7.41 (m, 1H, 7-H); 7.03-7.10 (m, 2H,5,6-H); 5.00 (m, 1H, 1-H), 2.81-2.87 (m, 1H, 4/4′-H), 2.70-2.74 (m, 1H,4′/4-H), 2.56 (br.s., 1H, OH), 2.17-2.21 (m, 2H, 2,2′-H), 1.74-1.79 (m,2H, 3,3′-H).

8-Bromo-3,4-dihydronaphthalen-1(2H)-one

To a solution of 56.0 g (250 mmol) of8-bromo-1,2,3,4-tetrahydronaphthalen-1-ol in 3500 mL of dichloromethanewas added 265 g (1.23 mol) of pyridinium chlorochromate (PCC). Theresulting mixture was stirred for 5 h at room temperature, then passedthrough a pad of silica gel 60 (500 mL; 40-63 um), and finallyevaporated to dryness. Yield 47.6 g (88%) of a colorless solid. ¹H NMR(CDCl₃): δ 7.53 (m, 1H, 7-H); 7.18-7.22 (m, 2H, 5,6-H); 2.95 (t, J=6.1Hz, 2H, 4,4′-H); 2.67 (t, J=6.6 Hz, 2H, 2,2′-H); 2.08 (quint, J=6.1 Hz,J=6.6 Hz, 2H, 3,3′-H).

(8-Bromo-1,2,3,4-tetrahydronaphthalen-1-yl)phenylamine

To a stirred solution of 21.6 g (232 mmol) of aniline in 140 mL oftoluene was added 10.93 g (57.6 mmol) of TiCl₄ over 30 min at roomtemperature under argon atmosphere. The resulting mixture was stirredfor 30 min at 90° C. followed by an addition of 13.1 g (57.6 mmol) of8-bromo-3,4-dihydronaphthalen-1(2H)-one. This mixture was stirred for 10min at 90° C., then cooled to room temperature, and poured into 500 mLof water. The product was extracted with 3×50 mL of ethyl acetate. Thecombined organic extract was dried over Na₂SO₄, evaporated to dryness,and the residue was re-crystallized from 10 mL of ethyl acetate. Theobtained crystalline solid was dissolved in 200 mL of methanol, 7.43 g(118 mmol) of NaBH₃CN and 3 mL of acetic acid were added in argonatmosphere. This mixture was heated to reflux for 3 h, then cooled toroom temperature, and evaporated to dryness. The residue was dilutedwith 200 mL of water, and crude product was extracted with 3×100 mL ofethyl acetate. The combined organic extract was dried over Na₂SO₄ andevaporated to dryness. The residue was purified by flash chromatographyon silica gel 60 (40-63 um, eluent: hexane-ethylacetate-triethylamine=100:10:1, vol.). Yield 13.0 g (75%) of a yellowoil. Anal. Calc. for Cl₆H₁₆BrN: C, 63.59; H, 5.34; N, 4.63. Found: C,63.82; H, 5.59; N, 4.49. ¹H NMR (CDCl₃): δ 7.44 (m, 1H), 7.21 (m, 2H),7.05-7.11 (m, 2H), 6.68-6.73 (m, 3H), 4.74 (m, 1H), 3.68 (br.s, 1H, NH),2.84-2.89 (m, 1H), 2.70-2.79 (m, 1H), 2.28-2.32 (m, 1H), 1.85-1.96 (m,1H), 1.76-1.80 (m, 1H), 1.58-1.66 (m, 1H).

N-Phenyl-8-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,2,3,4-tetrahydronaphthalen-1-amine

To a solution of 13.0 g (43.2 mmol) of(8-bromo-1,2,3,4-tetrahydronaphthalen-1-yl)phenylamine in 250 mL THF wasadded 17.2 mL (43.0 mmol) of 2.5 M ^(n)BuLi at −80° C. Further on, thismixture was stirred for 1 h at this temperature, and 56.0 mL (90.3 mmol)of 1.6 M ^(t)BuLi in pentane was added. The resulting mixture wasstirred for 1 h at the same temperature. Then, 16.7 g (90.0 mmol) of2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added. Afterthat the cooling bath was removed, and the resulting mixture was stirredfor 1 h at room temperature. Finally, 10 mL of water was added, and theobtained mixture was evaporated to dryness. The residue was diluted with200 mL of water, and crude product was extracted with 3×100 mL of ethylacetate. The combined organic extract was dried over Na₂SO₄ and thenevaporated to dryness. Yield 15.0 g (98%) of a yellow oil. Anal. Calc.for C₂₂H₂₈BNO₂: C, 75.65; H, 8.08; N, 4.01. Found: C, 75.99; H, 8.32; N,3.79. ¹H NMR (CDCl₃): δ 7.59 (m, 1H), 7.18-7.23 (m, 4H), 6.71-6.74 (m,3H), 5.25 (m, 1H), 3.87 (br.s, 1H, NH), 2.76-2.90 (m, 2H), 2.12-2.16 (m,1H), 1.75-1.92 (m, 3H), 1.16 (s, 6H), 1.10 (s, 6H).

2-(8-Anilino-5,6,7,8-tetrahydronaphthalen-1-yl)-N-(2,6-diisopropylphenyl)quinolin-8-amine(QDA-1)

To a solution of 13.8 g (41.0 mmol) of2-chloro-N-(2,6-diisopropylphenyl)quinolin-8-amine in 700 mL of1,4-dioxane were added 15.0 g (43.0 mmol) ofN-phenyl-8-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,2,3,4-tetrahydronaphthalen-1-amine,35.0 g (107 mmol) of cesium carbonate and 400 mL of water. The obtainedmixture was purged with argon for 10 min followed by an addition of 2.48g (2.15 mmol) of Pd(PPh₃)₄. The formed mixture was stirred for 2 h at90° C., then cooled to room temperature. To the obtained two-phasemixture 700 mL of n-hexane was added. The organic layer was separated,washed with brine, dried over Na₂SO₄, and then evaporated to dryness.The residue was purified by flash chromatography on silica gel 60 (40-63um, eluent: hexane-ethyl acetate-triethylamine=100:5:1, vol.) and thenre-crystallized from 150 mL of n-hexane. Yield 15.1 g (70%) of a yellowpowder. Anal. calc. for C₃₇H₃₉N₃: C, 84.53; H, 7.48; N, 7.99. Found: C,84.60; H, 7.56; N, 7.84. ¹H NMR (CDCl₃): δ 7.85-7.87 (d, J=7.98 Hz, 1H),7.56 (br.s, 1H), 7.43-7.45 (d, J=8.43 Hz, 1H), 7.21-7.38 (m, 6H), 7.12(t, J=7.77 Hz, 1H), 6.87-6.89 (d, J=7.99 Hz, 1H), 6.74 (t, J=7.99 Hz,1H), 6.36 (t, J=7.32 Hz, 1H), 6.14-6.21 (m, 3H), 5.35 (br.s, 1H), 3.56(br.s, 1H), 3.20-3.41 (m, 2H), 2.83-2.99 (m, 2H), 2.10-2.13 (m, 1H),1.77-1.92 (m, 3H), 1.13-1.32 (m, 12H).

Complex B: (QDA-1)HfMe₂

Benzene (50 mL) was added to QDA-1 (2.21 g, 4.20 mmol) andHf(NMe₂)₄(1.58 g, 4.45 mmol) to form a clear orange solution. Themixture was heated to reflux for 16 hours to form a clear red-orangesolution. Most of the volatiles were removed by evaporation under astream of nitrogen to afford a concentrated red solution (ca. 5 mL) thatwas warmed to 40° C. Then hexane (30 mL) was added and the mixture wasstirred to cause orange crystalline solid to form. This slurry wascooled to −40° C. for 30 minutes then the solid was collected byfiltration and washed with additional cold hexane (2×10 mL). Theresulting orange solid of (QDA-1)Hf(NMe₂)₂ was dried under reducedpressure (2.90 g, 3.67 mmol, 87.4% yield). This solid was dissolved intoluene (25 mL) and Me₃A1 (12.8 mL, 25.6 mmol) was added. The mixturewas warmed to 40° C. for 1 hour then evaporated under a stream ofnitrogen. The crude product (2.54 g) was ˜90% pure by HNMR spectroscopy.The solid was purified by recrystallization from CH₂Cl₂-hexanes (20mL-20 mL) by slow evaporation to give pure product as orange crystals(1.33 g, 43.2% from ligand). The mother liquor was further concentratedfor a second crop (0.291 g, 9.5% from ligand).

Polymerization Examples

Solutions of the pre-catalysts (complexes A and B) were made usingtoluene (ExxonMobil Chemical—anhydrous, stored under N2) (98%).Pre-catalyst solutions were typically 0.5 mmol/L.

Solvents, polymerization grade toluene and/or isohexanes were suppliedby ExxonMobil Chemical Co. and are purified by passing through a seriesof columns: two 500 cc Oxyclear cylinders in series from Labclear(Oakland, Calif.), followed by two 500 cc columns in series packed withdried 3 Å mole sieves (8-12 mesh; Aldrich Chemical Company), and two 500cc columns in series packed with dried 5 Å mole sieves (8-12 mesh;Aldrich Chemical Company).

1-octene (C8; 98%, Aldrich Chemical Company) was dried by stirring overNaK overnight followed by filtration through basic alumina (AldrichChemical Company, Brockman Basic 1).

Polymerization grade ethylene (C2) was used and further purified bypassing it through a series of columns: 500 cc Oxyclear cylinder fromLabclear (Oakland, Calif.) followed by a 500 cc column packed with dried3 Å mole sieves (8-12 mesh; Aldrich Chemical Company), and a 500 cccolumn packed with dried 5 Å mole sieves (8-12 mesh; Aldrich ChemicalCompany).

Polymerization grade propylene (C3) was used and further purified bypassing it through a series of columns: 2250 cc Oxiclear cylinder fromLabclear followed by a 2250 cc column packed with 3 Å mole sieves (8-12mesh; Aldrich Chemical Company), then two 500 cc columns in seriespacked with 5 Å mole sieves (8-12 mesh; Aldrich Chemical Company), thena 500 cc column packed with Selexsorb CD (BASF), and finally a 500 cccolumn packed with Selexsorb COS (BASF).

For polymerization runs collected in Tables 1, 4, and 6,bis(diisobutylaluminum)oxide (DiBAl-O, AkzoNobel 0.92M in hexane) wasused as a scavenger prior to introduction of the AVTA, activator andpre-catalyst into the reactor. Scavenger was typically used as a 5mmol/L solution in toluene.

Tri-n-octyl aluminum (TnOAl, neat, AkzoNobel) was used as a comparativeto the AVTA's and was typically used as a 5 or 10 mmol/L solution intoluene. The AVTA's were typically also used as a 5 or 10 mmol/Lsolution in toluene. AVTA# in Tables 1, 4, and 6, correspons to theAVTA's prepared in the examples above.

Reactor Description and Preparation:

Polymerizations were conducted in an inert atmosphere (N₂) drybox usingautoclaves equipped with an external heater for temperature control,glass inserts (internal volume of reactor=23.5 mL for C2 and C2/C8; 22.5mL for C3 and C2/C3 runs), septum inlets, regulated supply of nitrogen,ethylene and propylene, and equipped with disposable PEEK mechanicalstirrers (800 RPM). The autoclaves were prepared by purging with drynitrogen at 110° C. or 115° C. for 5 hours and then at 25° C. for 5hours.

Ethylene Polymerization (PE) or Ethylene/1-octene Copolymerization (EO):

The reactor was prepared as described above, and then purged withethylene. Isohexanes, 1-octene (50 μL for EO runs), and DiBAl-Oscavenger (0.05 umol) were added via syringe at room temperature andatmospheric pressure. The reactor was then brought to processtemperature (values indicated below) and charged with ethylene toprocess pressure (100 psig=790.8 kPa) while stirring at 800 RPM. TheAVTA solution was injected via syringe to the reactor at processconditions. Next, the activator solution, followed by the pre-catalystsolution, was injected via syringe to the reactor at process conditions.Ethylene was allowed to enter (through the use of computer controlledsolenoid valves) the autoclaves during polymerization to maintainreactor gauge pressure (+/−2 psig). Reactor temperature was monitoredand typically maintained within +/−1° C. Polymerizations were halted byaddition of approximately 50 psi O₂/Ar (5 mole % O₂) gas mixture to theautoclave for approximately 30 seconds. The polymerizations werequenched after a predetermined cumulative amount of ethylene had beenadded (maximum quench value in psid) or for a maximum of 30 minutespolymerization time. Afterwards, the reactors were cooled and vented.Polymers were isolated after the solvent was removed in-vacuo. Yieldsreported include total weight of polymer and residual catalyst. Catalystactivity is reported as grams of polymer per mmol transition metalcompound per hour of reaction time (g/mmol*hr). Ethylenehomopolymerization runs and ethylene/1-octene copolymerization runs aresummarized in Table 6.

Ethylene-Propylene Copolymerization (EP):

The reactor was prepared as described above, then heated to 40° C., andthen purged with ethylene gas at atmospheric pressure. Ethylene was thenadded at 125 psid (790.8 kPa) to the reactor. Isohexanes and scavenger(DiBAl-O, 0.5 μmol) were added via syringe. The stirrers were thenstarted and maintained at 800 RPM. Liquid propylene (0.5 ml) was theninjected into the reactor. The reactor was then brought to processtemperature (85° C. or 100° C.). The AVTA or control TnOAl solutionswere next injected into the reactor at process temperature. Next, theactivator solution, followed by the pre-catalyst solution, was injectedvia syringe to the reactor at process conditions. Reactor temperaturewas monitored and typically maintained within +/−1° C. Polymerizationswere halted by addition of approximately 50 psi O2/Ar (5 mole % O2) gasmixture to the autoclaves for approximately 30 seconds. Thepolymerizations were quenched based on a predetermined pressure loss(quench value) of approximately 4 psid pressure loss or for a maximum of30 minutes polymerization time. The reactors were cooled and vented. Thepolymer was isolated after the solvent was removed in-vacuo. The quenchtimes are reported in Table 1 for each run. Yields reported includetotal weight of polymer and residual catalyst. Catalyst activity isreported as grams of polymer per mmol transition metal compound per hourof reaction time (g/mmol*hr). Ethylene/propylene copolymerizationexamples are collected in Table 1 and additional information is locatedabove the table.

Propylene Homopolymerization (PP):

The reactor was prepared as described above, then heated to 40° C., andthen purged with propylene gas at atmospheric pressure. Isohexanes,propylene (1.0 ml) and scavenger (DiBAl-O, 0.5 μmol) were added viasyringe. The reactor was then brought to process temperature (85° C. or100° C.) while stirring at 800 RPM. The AVTA or control TnOAl solutionswere next injected into the reactor at process temperature. Theactivator solution, followed by the pre-catalyst solution, were injectedvia syringe to the reactor at process conditions. Reactor temperaturewas monitored and typically maintained within +/−1° C. Polymerizationswere halted by addition of approximately 50 psi O₂/Ar (5 mole % O₂) gasmixture to the autoclaves for approximately 30 seconds. Thepolymerizations were quenched based on a predetermined pressure loss ofapproximately 8 psid (max quench value in psi) loss, or for a maximum of30 minutes polymerization time. The reactors were cooled and vented. Thepolymers were isolated after the solvent was removed in-vacuo. Theactual quench times are reported in Table 4 for each run. Yieldsreported include total weight of polymer and residual catalyst. Catalystactivity is reported as grams of polymer per mmol transition metalcompound per hour of reaction time (g/mmol*hr). Propylenehomopolymerization examples are reported in Table 4 and additionalinformation is located above the table.

Polymer Characterization

For analytical testing, polymer sample solutions were prepared bydissolving polymer in 1,2,4-trichlorobenzene (TCB, 99+% purity fromSigma-Aldrich) containing 2,6-di-tert-butyl-4-methylphenol (BHT, 99%from Aldrich) at 165° C. in a shaker oven for approximately 3 hours. Thetypical concentration of polymer in solution was between 0.1 to 0.9mg/mL with a BHT concentration of 1.25 mg BHT/mL of TCB. Samples werecooled to 135° C. for testing.

High temperature size exclusion chromatography was performed using anautomated “Rapid GPC” system as described in U.S. Pat. Nos. 6,491,816;6,491,823; 6,475,391; 6,461,515; 6,436,292; 6,406,632; 6,175,409;6,454,947; 6,260,407; and 6,294,388; each of which is incorporatedherein by reference. Molecular weights (weight average molecular weight(Mw) and number average molecular weight (Mn)) and molecular weightdistribution (MWD=Mw/Mn), which is also sometimes referred to as thepolydispersity (PDI) of the polymer, were measured by Gel PermeationChromatography using a Symyx Technology GPC equipped with dualwavelength infrared detector and calibrated using polystyrene standards(Polymer Laboratories: Polystyrene Calibration Kit S-M-10: Mp (peak Mw)between 580 and 3,039,000). Samples (250 μL of a polymer solution in TCBwere injected into the system) were run at an eluent flow rate of 2.0mL/minute (135° C. sample temperatures, 165° C. oven/columns) usingthree Polymer Laboratories: PLgel 10 μm Mixed-B 300×7.5 mm columns inseries. No column spreading corrections were employed. Numericalanalyses were performed using Epoch® software available from SymyxTechnologies or Automation Studio software available from Freeslate. Themolecular weights obtained are relative to linear polystyrene standards.Molecular weight data is reported in Tables 1, 4 and 6 under theheadings Mn, Mw and PDI (or Mw/Mn) as defined above.

Differential Scanning Calorimetry (DSC) measurements were performed on aTA-Q100 instrument to determine the melting point of the polymers.Samples were pre-annealed at 220° C. for 15 minutes and then allowed tocool to room temperature overnight. The samples were then heated to 220°C. at a rate of 100° C./minute and then cooled at a rate of 50°C./minute. Melting points were collected during the heating period forthe second melt. The results are reported in the Tables 1, 4 and 6 underthe heading, Tm (° C.).

Samples for infrared analysis were prepared by depositing the stabilizedpolymer solution onto a silanized wafer (Part number S10860, Symyx). Bythis method, approximately between 0.12 and 0.24 mg of polymer isdeposited on the wafer cell. The samples were subsequently analyzed on aBrucker Equinox 55 FTIR spectrometer equipped with Pikes' MappIRspecular reflectance sample accessory. Spectra, covering a spectralrange of 5000 cm⁻¹ to 500 cm⁻¹, were collected at a 2 cm⁻¹ resolutionwith 32 scans.

For ethylene-1-octene copolymers, the wt % octene in the copolymer wasdetermined via measurement of the methyl deformation band at −1375 cm⁻¹.The peak height of this band was normalized by the combination andovertone band at −4321 cm⁻¹, which corrects for path length differences.The normalized peak height was correlated to individual calibrationcurves from ¹H NMR data to predict the wt % octene content within aconcentration range of −2 to 35 wt % for octene. Typically, R²correlations of 0.98 or greater are achieved. (These numbers arereported in Table 6 under the heading C8 wt %.)

Unless otherwise indicated, proton NMR spectra are collected using a 400MHz Varian pulsed fourier transform NMR spectrometer equipped with avariable temperature proton detection probe operating at 120° C. Thepolymer sample is dissolved in 1,1,2,2-tetrachloroethane-d2 (TCE-d2) andtransferred into a 5 mm glass NMR tube. Typical acquisition parametersare sweep width=10 KHz, pulse width=30 degrees, acquisition time=2 s,acquisition delay=5 s and number of scans=120. Chemical shifts aredetermined relative to the TCE-d2 signal which is set to 5.98 ppm.

The chain end unsaturations are determined as follows. The vinylresonances of interest are between from about 5.0 to 5.1 ppm (VRA), thevinylidene resonances between from about 4.65 to 4.85 ppm (VDRA), thevinylene resonances from about 5.31 to 5.55 ppm (VYRA), thetri-substituted unsaturated species from about 5.11 to 5.30 ppm (TSRA)and the aliphatic region of interest between from about 0 to 2.1 ppm(IA). The number of vinyl groups/1000 Carbons is determined from theformula: (VRA*500)/((IA+VRA+VYRA+VDRA)/2)+TSRA). Likewise, the number ofvinylidene groups/1000 Carbons is determined from the formula:(VDRA*500)/((IA+VRA+VYRA+VDRA)/2)+TSRA), the number of vinylenegroups/1000 Carbons from the formula(VYRA*500)/((IA+VRA+VYRA+VDRA)/2)+TSRA) and the number oftri-substituted groups from the formula(TSRA*1000)/((IA+VRA+VYRA+VDRA)/2)+TSRA). VRA, VDRA, VYRA, TSRA and IAare the integrated normalized signal intensities in the chemical shiftregions defined above. Proton NMR data is reported in Tables 2 and 5.For many examples, end-group unsaturation was below the detection limit,or noise level, and could not be determined.

GPC3D data is reported in Table 3 and is described further below.

For the polymerization results collected in the Tables below, “Ex#”stands for example number. Under the Ex# column heading, the followingabbreviations are defined: PE=polyethylene, EO=ethylene-1-octenecopolymer, PP=polypropylene and EP=ethylene-propylene copolymer, TMCidentifies the pre-catalyst/complex used, T (° C.) is the polymerizationtemperature which was typically maintained within +/−1° C. “Yield” ispolymer yield, and is not corrected for catalyst residue. “Quench time(s)” is the actual duration of the polymerization run in seconds.“Quench Value (psid)” for ethylene based polymerization runs (nopropylene) is the set maximum amount of ethylene uptake (conversion) forthe experiment. If a polymerization quench time is less than the maximumtime set, then the polymerization ran until the set maximum value ofethylene uptake was reached. For ethylene-propylene copolymerizationruns, quench value indicates the maximum set pressure loss (conversion)of ethylene and propylene combined during the polymerization. Forpropylene homopolymerization runs, quench value indicates the maximumset pressure loss (conversion) of propylene during the polymerization.Activity is reported at grams polymer per mmol of catalyst per hour.

TABLE 1 High throughput ethylene-propylene (EP) runs using tri-n-octylaluminum (TNOAl) or AVTA1. Conditions: For all examples in Table 1,0.025 μmol of complex A was used as the pre-catalyst and activated with1.1 molar equivalents of dimethylaniliniumtetrakis(pentafluorophenyl)borane. Propylene (0.5 ml) was added, and thetotal reagent and solvent volume in the reactor was 5 ml. All runsutilized 0.05 μmol of bis(diisobutyl aluminum)oxide as scavenger.Ethylene (125 psid) was added before catalyst injection and no furtherethylene was added to the reactor. The run was quenched after 4 psid(Quench Value) of reactor pressure loss. Maximum quench time was set to30 minutes. AVTA AVTA or Iso- Activity (g PDI or TnOAl hexane Toluene Tquench yield P/mmol Mn Mw Mz (Mw/ Tm Ex# TnOAl (umol) (uL) (uL) (° C.)time (s) (g) cat · hr) (g/mol) (g/mol) (g/mol) Mn) (° C.) EP-1 TNOAL0.251 4103 272 85 23 0.1493 934,748 292,208 535,733 1,054,060 1.83 46.6EP-2 TNOAL 1.001 3952 422 85 6 0.1445 3,468,000 117,860 176,507 308,4651.50 44.4 EP-3 TNOAL 2.001 3752 622 85 3 0.1558 7,478,400 68,276 100,143170,786 1.47 44.6 EP-4 TNOAL 0.251 4103 272 100 25 0.1323 762,048276,616 449,079 850,755 1.62 46.6 EP-5 TNOAL 1.001 3952 422 100 4 0.12534,510,800 94,215 146,449 267,283 1.55 46.3 EP-6 TNOAL 2.001 3752 622 1003 0.1278 6,134,400 60,138 87,166 159,408 1.45 44.5 EP-7 TNOAL 2.501 3903471 85 3 0.1568 7,526,400 54,180 77,479 130,584 1.43 42.9 EP-8 TNOAL3.501 3802 571 85 3 0.1557 7,473,600 43,016 61,457 102,806 1.43 43.5EP-9 TNOAL 4.001 3752 621 85 3 0.1486 7,132,800 36,797 51,760 85,4481.41 44.0 EP-10 TNOAL 2.501 3903 471 100 3 0.1344 6,451,200 46,29066,224 109,631 1.43 44.0 EP-11 TNOAL 3.501 3802 571 100 2 0.13389,633,600 35,040 50,519 88,353 1.44 43.5 EP-12 TNOAL 4.001 3752 621 1002 0.1288 9,273,600 32,889 46,253 79,734 1.41 44.7 EP-13 AVTA1 0.251 4103272 85 25 0.1566 902,016 463,034 926,140 2,022,783 2.00 48.0 EP-14 AVTA10.501 4053 322 85 34 0.1596 675,953 420,892 699,328 1,265,888 1.66 48.5EP-15 AVTA1 1.001 3953 422 85 29 0.1578 783,559 239,097 437,480 888,2191.83 46.3 EP-16 AVTA1 0.251 4103 272 100 34 0.1258 532,800 341,323703,230 1,518,486 2.06 47.5 EP-17 AVTA1 0.501 4053 322 100 38 0.1397529,389 293,966 532,964 1,036,153 1.81 47.7 EP-18 AVTA1 1.001 3953 422100 9 0.1197 1,915,200 202,179 352,395 714,063 1.74 49.4 EP-19 AVTA10.251 4103 272 85 27 0.1539 820,800 438,042 975,027 2,407,966 2.23 48.3EP-20 AVTA1 0.501 4053 322 85 38 0.1575 596,842 434,287 797,3401,957,466 1.84 48.9 EP-21 AVTA1 1.001 3953 422 85 39 0.1443 532,800303,658 501,177 1,015,472 1.65 48.3 EP-22 AVTA1 0.251 4103 272 100 460.1309 409,774 365,325 767,535 1,716,813 2.10 47.5 EP-23 AVTA1 0.5014053 322 100 34 0.1375 582,353 304,461 595,080 1,311,158 1.95 47.6 EP-24AVTA1 1.001 3953 422 100 14 0.1259 1,294,971 237,702 409,097 925,6701.72 46.3 EP-25 AVTA1 1.501 3852 522 85 13 0.1338 1,482,092 203,610348,970 758,806 1.71 46.8 EP-26 AVTA1 2.001 3752 622 85 9 0.12161,945,600 170,457 286,096 610,025 1.68 45.2 EP-27 AVTA1 2.501 3902 47285 7 0.1478 3,040,457 106,614 186,693 410,714 1.75 45.4 EP-28 AVTA11.501 3852 522 100 7 0.1112 2,287,543 157,969 278,726 573,185 1.76 46.3EP-29 AVTA1 2.001 3752 622 100 6 0.1003 2,407,200 126,624 217,002433,449 1.71 44.6 EP-30 AVTA1 2.501 3902 472 100 4 0.1271 4,575,60093,687 153,141 314,987 1.63 44.7 EP-31 AVTA1 1.501 3852 522 85 5 0.09742,805,120 150,379 273,127 701,611 1.82 44.2 EP-32 AVTA1 2.001 3752 62285 7 0.1189 2,445,943 153,765 274,790 614,577 1.79 44.0 EP-33 AVTA12.501 3902 472 85 6 0.1518 3,643,200 100,044 189,835 448,573 1.90 43.9EP-34 AVTA1 1.501 3852 522 100 8 0.1092 1,965,600 159,136 282,274617,642 1.77 47.1 EP-35 AVTA1 2.001 3752 622 100 6 0.0975 2,340,000123,227 216,535 482,359 1.76 49.0 EP-36 AVTA1 2.501 3902 472 100 40.1238 4,456,800 87,342 155,183 356,179 1.78 45.1 EP-37 AVTA1 3.001 3853521 85 7 0.1061 2,182,629 76,426 132,373 276,128 1.73 44.0 EP-38 AVTA13.501 3803 571 85 7 0.1029 2,116,800 75,629 128,342 273,071 1.70 44.4EP-39 AVTA1 4.001 3752 621 85 6 0.0979 2,349,600 62,586 114,406 266,0211.83 43.2 EP-40 AVTA1 3.001 3853 521 100 4 0.1166 4,197,600 69,880121,293 265,051 1.74 46.1 EP-41 AVTA1 3.501 3803 571 100 3 0.11575,553,600 63,137 104,149 204,886 1.65 44.7 EP-42 AVTA1 4.001 3752 621100 3 0.1225 5,880,000 57,723 97,341 200,023 1.69 43.7 EP-43 AVTA1 3.0013853 521 85 7 0.1044 2,147,657 74,592 128,605 289,895 1.72 44.2 EP-44AVTA1 3.501 3803 571 85 6 0.1083 2,599,200 77,638 123,454 255,841 1.5942.9 EP-45 AVTA1 4.001 3752 621 85 7 0.1002 2,061,257 59,533 99,716201,140 1.67 43.7 EP-46 AVTA1 3.001 3853 521 100 4 0.1020 3,672,00063,582 114,103 262,787 1.79 44.9 EP-47 AVTA1 3.501 3803 571 100 4 0.10933,934,800 57,802 101,911 237,121 1.76 44.9 EP-48 AVTA1 4.001 3752 621100 4 0.0950 3,420,000 54,987 90,747 202,879 1.65 44.6

TABLE 2 ¹H NMR data for select EP samples from Table 1. C3 vinylenes/trisubs/ vinyls/ vinylidene/ Ex# C3 (mol %) (wt %) 1000 C. 1000 C. 1000C. 1000 C. % vinyl EP-2 25.4 33.8 EP-5 23 30.9 EP-9 23.7 31.8 EP-13 36.646.4 EP-14 36.1 45.9 EP-15 33.3 42.8 EP-18 24.0 32.2 EP-25 25.0 33.4EP-27 25.7 34.2 0 0 0.17 0.01 94 EP-28 21.4 29.0 0.02 0.05 0.14 0.01 64EP-29 19.5 26.6 0.01 0.02 0.20 0.01 83 EP-30 23.6 31.7 0.01 0.01 0.200.01 87 EP-32 20.7 28.1 0 0.02 0.19 0.02 83 EP-37 19.5 26.6 0 0.01 0.340.02 92 EP-38 18.9 25.9 0.01 0.03 0.39 0.02 87 EP-39 19.4 26.6 0.01 0.060.41 0.02 82 EP-40 23.2 31.2 0 0.01 0.29 0.03 88 EP-41 22.4 30.2 0.020.03 0.35 0.03 81 EP-42 22.9 30.8 0.02 0.05 0.39 0.03 80

TABLE 3 GPC 3D data for select EP samples from Table 1. GPC LS GPC LSGPC LS GPC GPC GPC GPC DRI GPC GPC LS Mw Mz Mv LS DRI Mn DRI Mw Mz DRIEx# Mn (g/mol) (g/mol) (g/mol) Mw/Mn g′ (vis) (g/mol) (g/mol) (g/mol)Mw/Mn EP-2 45,749 75,656 102,109 71,410 1.65 0.973 42,056 83,423 127,1691.98 EP-5 42,524 64,596 86,719 61,310 1.52 0.978 40,855 69,615 101,3231.70 EP-9 15,076 22,003 29,224 20,931 1.46 0.959 14,245 24,322 34,9701.71 EP-13 200,401 485,104 813,916 440,475 2.42 1.106 169,293 494,592894,116 2.92 EP-14 153,453 319,947 528,962 292,329 2.08 1.071 134,741335,830 601,817 2.49 EP-15 124,856 228,765 363,099 211,482 1.83 1.012112,999 240,663 410,141 2.13 EP-18 101,088 173,934 258,316 162,146 1.720.976 89,517 86,933 326,829 0.97 EP-25 92,303 154,284 227,004 144,1841.67 0.970 84,399 167,134 284,644 1.98 EP-27 49,886 83,490 125,54277,820 1.67 0.920 43,107 87,464 145,405 2.03 EP-28 67,954 117,653173,671 109,406 1.73 0.940 52,636 130,672 227,052 2.48 EP-29 55,38996,175 142,735 89,717 1.74 0.956 51,502 103,475 176,723 2.01 EP-3040,554 68,178 105,771 63,292 1.68 0.939 37,005 71,052 115,499 1.92 EP-3265,328 119,979 186,254 111,190 1.84 0.963 56,594 123,948 207,881 2.19EP-37 33,996 57,916 86,755 54,031 1.70 0.943 31,285 60,328 85,248 1.93EP-38 33,110 51,615 78,644 48,185 1.56 0.924 25,600 54,255 97,298 2.12EP-39 25,666 45,216 72,856 41,694 1.76 0.940 21,119 47,778 78,324 2.26EP-40 33,496 52,525 78,351 49,172 1.57 0.918 28,639 55,401 91,127 1.93EP-41 26,755 46,640 71,332 42,328 1.74 0.927 24,627 48,516 78,716 1.97EP-42 23,546 40,798 60,714 37,958 1.73 0.921 22,168 14,133 73,735 0.64

TABLE 4 High throughput polypropylene (PP) runs using tri-n-octylaluminum (TNOAl) or AVTA1. Conditions: For all examples in Table 4,0.025 μmol of catalyst A was used and activated with 1.1 molarequivalents of dimethylanilinium tetrakis(pentafluorophenyl)borane.Propylene (1.0 ml) was added, and the total reagent and solvent volumein the reactor was 5 ml. All runs utilized 0.05 μmol of bis(diisobutylaluminum)oxide as scavenger. The run was quenched after 8 psid (QuenchValue) of reactor pressure loss. Maximum quench time was set to 30minutes. AVTA AVTA or Iso- Activity PDI or TnOAl hexane Toluene T quenchyield (g P/mmol Mn Mw Mz (Mw/ Tm Ex# TnOAl (umol) (uL) (uL) (° C.) time(s) (g) cat · hr) (g/mol) (g/mol) (g/mol) Mn) (° C.) PP-1 TNOAL 0.2513728 272 85 159 0.1061 96,091 326,036 599,058 1,327,264 1.84 110.8 PP-2TNOAL 1.001 3577 422 85 109 0.1071 141,490 94,099 224,867 612,641 2.39112.3 PP-3 TNOAL 2.001 3377 622 85 106 0.1133 153,917 64,946 146,804379,705 2.26 112.5 PP-4 TNOAL 0.251 3728 272 100 168 0.0840 72,000147,585 285,569 612,176 1.93 108.3 PP-5 TNOAL 1.001 3577 422 100 1870.0965 74,310 69,554 157,043 387,807 2.26 111.7 PP-6 TNOAL 2.001 3377622 100 193 0.0949 70,806 45,382 97,712 231,172 2.15 109.8 PP-7 TNOAL2.501 3528 471 85 103 0.1112 155,464 40,672 98,015 269,188 2.41 114.8PP-8 TNOAL 3.501 3427 571 85 108 0.1091 145,467 32,326 71,934 173,7852.23 114.8 PP-9 TNOAL 4.001 3377 621 85 146 0.0989 97,545 22,325 57,107150,074 2.56 115.3 PP-10 TNOAL 2.501 3528 471 100 200 0.0837 60,26429,255 69,990 196,565 2.39 111.6 PP-11 TNOAL 3.501 3427 571 100 2140.0763 51,342 18,559 47,071 121,149 2.54 112.5 PP-12 TNOAL 4.001 3377621 100 261 0.0852 47,007 13,290 45,031 139,094 3.39 110.2 PP-13 AVTA10.251 3728 272 85 110 0.1239 162,196 421,928 665,688 1,195,227 1.58109.8 PP-14 AVTA1 0.501 3678 322 85 107 0.1099 147,903 289,920 513,2161,006,023 1.77 109.8 PP-15 AVTA1 1.001 3578 422 85 113 0.1112 141,706163,141 363,919 931,001 2.23 110.5 PP-16 AVTA1 0.251 3728 272 100 2850.0831 41,987 276,208 434,453 858,574 1.57 107.5 PP-17 AVTA1 0.501 3678322 100 184 0.0869 68,009 188,589 326,775 691,293 1.73 108.0 PP-18 AVTA11.001 3578 422 100 267 0.0844 45,519 139,376 241,141 557,012 1.73 108.8PP-19 AVTA1 0.251 3728 272 85 109 0.1166 154,040 372,738 665,5661,504,064 1.79 110.1 PP-20 AVTA1 0.501 3678 322 85 141 0.1093 111,626305,325 553,453 1,210,448 1.81 110.3 PP-21 AVTA1 1.001 3578 422 85 1470.1065 104,327 183,136 363,345 842,161 1.98 109.7 PP-22 AVTA1 0.251 3728272 100 189 0.0876 66,743 250,868 427,830 916,725 1.71 107.4 PP-23 AVTA10.501 3678 322 100 158 0.0894 81,478 169,871 340,811 855,226 2.01 108.7PP-24 AVTA1 1.001 3578 422 100 225 0.0880 56,320 120,925 241,777 592,9702.00 109.3 PP-25 AVTA1 1.501 3477 522 85 145 0.1016 100,899 114,033253,279 644,428 2.22 109.2 PP-26 AVTA1 2.001 3377 622 85 129 0.0973108,614 102,296 238,019 693,801 2.33 111.3 PP-27 AVTA1 2.501 3527 472 8598 0.1040 152,816 62,613 173,075 585,931 2.76 112.1 PP-28 AVTA1 1.5013477 522 100 235 0.0852 52,208 98,603 196,899 543,333 2.00 109.5 PP-29AVTA1 2.001 3377 622 100 239 0.0834 50,249 82,144 159,362 415,328 1.94109.8 PP-30 AVTA1 2.501 3527 472 100 184 0.0881 68,948 60,406 127,338334,440 2.11 110.3 PP-31 AVTA1 1.501 3477 522 85 94 0.0882 135,115137,115 250,275 581,536 1.83 111.5 PP-32 AVTA1 2.001 3377 622 85 1430.0987 99,390 119,318 228,913 566,669 1.92 111.9 PP-33 AVTA1 1.501 3477522 100 234 0.0856 52,677 95,389 196,214 529,556 2.06 109.7 PP-34 AVTA12.001 3377 622 100 312 0.0775 35,769 85,472 145,777 320,873 1.71 109.5PP-35 AVTA1 2.501 3527 472 100 195 0.0880 64,985 54,458 128,778 394,1842.36 111.0 PP-36 AVTA1 3.001 3478 521 85 114 0.0991 125,179 60,872138,579 372,932 2.28 113.5 PP-37 AVTA1 3.501 3428 571 85 101 0.0995141,861 58,257 127,761 348,336 2.19 112.8 PP-38 AVTA1 4.001 3377 621 85100 0.1027 147,888 59,717 128,175 396,107 2.15 111.8 PP-39 AVTA1 3.0013478 521 100 204 0.0881 62,188 55,202 107,936 255,371 1.96 110.7 PP-40AVTA1 3.501 3428 571 100 198 0.0836 60,800 46,327 94,344 235,381 2.04109.5 PP-41 AVTA1 4.001 3377 621 100 210 0.0845 57,943 34,378 82,191208,755 2.39 108.9 PP-42 AVTA1 3.001 3478 521 85 100 0.0899 129,45656,289 131,849 351,616 2.34 112.2 PP-43 AVTA1 3.501 3428 571 85 1150.1010 126,470 75,730 133,774 286,336 1.77 113.5 PP-44 AVTA1 4.001 3377621 85 121 0.1072 127,577 59,037 127,326 341,903 2.16 112.8 PP-45 AVTA13.001 3478 521 100 209 0.0827 56,980 47,563 99,561 236,847 2.09 110.3PP-46 AVTA1 3.501 3428 571 100 267 0.0806 43,470 38,133 86,432 227,0942.27 109.7 PP-47 AVTA1 4.001 3377 621 100 246 0.0775 45,366 35,93377,372 187,787 2.15 109.5

TABLE 5 ¹H NMR data for select PP samples from Table 4. vinylenes/trisubs/ vinyls/ vinylidenes/ Ex# 1000 C 1000 C 1000 C 1000 C % vinylPP-2 0.04 0.14 0.09 0.16 21* PP-5 0.04 0.19 0.12 0.20 22  PP-9 0.13 0.490.25 0.33 21* PP-12 0.00 0.33 0.23 0.28 27* PP-13 0.07 0.17 0.12 0.2320  PP-14 0.03 0.09 0.08 0.12 25  PP-15 0.01 0.06 0.07 0.10 29  PP-220.05 0.15 0.10 0.17 21  PP-23 0.04 0.09 0.07 0.08 25* PP-24 0.05 0.100.09 0.09 27* PP-25 0.01 0.05 0.10 0.09 40* PP-27 0.01 0.03 0.14 0.0464* PP-29 0.10 0.16 0.35 0.12 48* PP-32 0.01 0.03 0.09 0.04 53* PP-330.08 0.11 0.20 0.08 43* PP-35 0.08 0.13 0.32 0.10 51* PP-36 0.00 0.050.26 0.05 72* PP-39 0.04 0.05 0.34 0.10 64* PP-40 0.07 0.15 0.53 0.1559* PP-41 0.09 0.24 1.04 0.26 64* PP-43 0.13 0.29 0.48 0.14 46* PP-440.02 0.05 0.24 0.04 69* *indicates that the ¹H NMR baseline was noisy.

TABLE 6 High throughput polyethylene (PE) and ethylene-octene (EO) runsusing tri-n-octyl aluminum (TNOAl), AVTA2 or AVTA3. Conditions: For allexamples in Table 46, 0.020 μmol of catalyst A or B was used andactivated with 1.1 molar equivalents of dimethylaniliniumtetrakis(pentafluorophenyl)borane. 1-octene (50 μmol) was added for EOpolymerizations, and the total reagent and solvent volume in the reactorwas 5 ml. All runs utilized 0.05 μmol of bis(diisobutyl aluminum)oxideas scavenger. The run was quenched after 20 psid (Quench Value) ofethylene uptake. Maximum quench time was set to 30 minutes. ActivityIso- Tol- (g PDI AVTA hexane uene quench T yield P/mmol Mn Mw Mz (Mw/ C8Tm Ex# TMC AVTA (umol) (uL) (uL) time (s) (° C.) (g) cat · hr) (g/mol)(g/mol) (g/mol) Mn) (wt %) (° C.) EO-1 A AVTA3 0.501 4731 219 153 850.1220 143,529 361,321 907,576 3,376,196 2.51 17.9 107.4 PE-1 A AVTA32.501 4381 618 23 85 0.0909 711,391 65,067 106,506 217,566 1.64 0 134.1PE-2 A AVTA2 2.501 4381 618 37 85 0.1048 509,838 120,654 228,556 595,3581.89 0 132.6 EO-2 A AVTA3 0.501 4731 219 186 100 0.1113 107,710 285,786500,423 1,172,199 1.75 20.7 101.2 PE-3 A AVTA3 2.501 4381 618 21 1000.0676 579,429 45,404 72,290 154,618 1.59 0 132.5 PE-4 A AVTA2 2.5014381 618 21 100 0.0898 769,714 83,185 144,060 309,560 1.73 0 132.4 EO-3A AVTA3 1.001 4631 318 153 85 0.1205 141,765 184,321 338,318 828,8371.84 18.1 105.0 EO-4 A AVTA3 1.501 4531 418 37 85 0.1180 574,054 121,905222,546 574,863 1.83 14.1 106.7 EO-5 A AVTA2 1.501 4531 418 99 85 0.1196217,455 179,452 321,463 745,551 1.79 19.9 106.2 EO-6 A AVTA3 1.001 4631318 32 100 0.0910 511,875 131,426 205,789 428,507 1.57 14.6 101.5 EO-7 AAVTA3 1.501 4531 418 23 100 0.0810 633,913 76,659 120,969 244,923 1.5812.6 105.3 EO-8 A AVTA2 1.501 4531 418 30 100 0.0976 585,600 119,755209,324 494,755 1.75 12.9 100.9 EO-9 A AVTA2 0.501 4731 219 164 850.1187 130,280 393,699 772,879 2,067,033 1.96 20.4 105.0 EO-10 A AVTA32.001 4431 518 25 85 0.1014 730,080 86,466 134,196 268,756 1.55 10.9110.6 EO-11 A AVTA2 2.001 4431 518 38 85 0.1174 556,105 133,985 248,579621,633 1.86 16.3 106.2 EO-12 A AVTA2 0.501 4731 219 56 100 0.0918295,071 273,603 496,511 1,167,847 1.81 18.5 97.9 EO-13 A AVTA3 2.0014431 518 24 100 0.0712 534,000 54,064 87,965 194,251 1.63 11.4 111.4EO-14 A AVTA2 2.001 4431 518 27 100 0.0969 646,000 95,278 166,714426,502 1.75 13.2 104.5 EO-15 A AVTA2 1.001 4631 319 113 85 0.1169186,212 235,798 437,689 985,772 1.86 18.6 105.9 EO-16 A AVTA3 2.501 4331618 24 85 0.0828 621,000 56,758 96,651 196,361 1.70 8.1 116.4 EO-17 AAVTA2 2.501 4331 618 24 85 0.1106 829,500 97,090 167,251 363,833 1.7214.5 108.1 EO-18 A AVTA2 1.001 4631 319 40 100 0.0918 413,100 165,756298,665 737,468 1.80 18.3 101.5 EO-19 A AVTA3 2.501 4331 618 22 1000.0687 562,091 49,197 72,635 138,884 1.48 5.6 117.3 EO-20 A AVTA2 2.5014331 618 21 100 0.0864 740,571 73,119 124,550 352,065 1.70 10.3 109.2EO-21 B AVTA3 0.501 4731 219 77 85 0.0564 131,844 294,032 497,2831,000,672 1.69 8.9 113.2 PE-5 B AVTA3 2.501 4381 618 22 85 0.0850695,455 71,836 128,242 277,907 1.79 0 133.8 PE-6 B AVTA2 2.501 4381 61825 85 0.0963 693,360 119,738 258,807 694,257 2.16 0 131.9 EO-22 B AVTA30.501 4731 219 43 100 0.0959 401,442 277,805 502,086 1,207,864 1.81 15.7103.1 PE-7 B AVTA3 2.501 4381 618 22 100 0.0679 555,545 53,053 87,222176,276 1.64 0 132.7 PE-8 B AVTA2 2.501 4381 618 22 100 0.0845 691,36478,787 153,194 377,095 1.94 0 132.2 EO-23 B AVTA3 1.001 4631 318 44 850.1045 427,500 191,683 357,743 786,227 1.87 12.3 107.9 EO-24 B AVTA31.501 4531 418 29 85 0.0749 464,897 112,541 185,327 392,724 1.65 7.9113.4 EO-25 B AVTA2 1.501 4531 418 34 85 0.0989 523,588 190,387 342,189743,452 1.80 11.6 109.6 EO-26 B AVTA3 1.001 4631 318 34 100 0.0761402,882 130,891 212,894 476,552 1.63 9.6 109.7 EO-27 B AVTA3 1.501 4531418 26 100 0.0830 574,615 95,662 163,687 383,864 1.71 8.6 112.3 EO-28 BAVTA2 1.501 4531 418 32 100 0.0881 495,563 129,555 231,671 540,891 1.799.3 109.8 EO-29 B AVTA2 0.501 4731 219 115 85 0.0954 149,322 483,002890,657 2,223,574 1.84 14.1 107.4 EO-30 B AVTA3 2.001 4431 518 30 850.0654 392,400 77,063 137,500 307,605 1.78 5.9 118.6 EO-31 B AVTA2 2.0014431 518 28 85 0.1011 649,929 144,858 267,417 637,823 1.85 11.6 110.5EO-32 B AVTA2 0.501 4731 219 35 100 0.0892 458,743 324,062 615,8651,383,659 1.90 15.2 104.8 EO-33 B AVTA3 2.001 4431 518 23 100 0.0776607,304 69,660 120,856 264,994 1.73 4.2 122.5 EO-34 B AVTA2 2.001 4431518 32 100 0.0685 385,313 74,522 146,160 376,116 1.96 5.8 119.9 EO-35 BAVTA2 1.001 4631 319 38 85 0.0862 408,316 254,934 438,047 960,665 1.728.1 112.2 EO-36 B AVTA3 2.501 4331 618 41 85 0.0551 241,902 73,850115,997 253,515 1.57 4.6 121.6 EO-37 B AVTA2 2.501 4331 618 27 85 0.0980653,333 126,895 241,187 571,676 1.90 9.3 113.4 EO-38 B AVTA2 1.001 4631319 35 100 0.0819 421,200 152,389 307,178 724,831 2.02 11.7 109.3 EO-39B AVTA3 2.501 4331 618 20 100 0.0680 612,000 46,839 81,397 165,173 1.743.6* 123.6 EO-40 B AVTA2 2.501 4331 618 22 100 0.0882 721,636 81,212162,758 433,899 2.00 8.6 113.5 *octene content by FTIR is outside of thecalibration range

Unless otherwise indicated, proton NMR spectra are collected using a 400MHz Varian pulsed fourier transform NMR spectrometer equipped with avariable temperature proton detection probe operating at 120° C. Thepolymer sample is dissolved in 1,1,2,2-tetrachloroethane-d2 (TCE-d2) andtransferred into a 5 mm glass NMR tube. Typical acquisition parametersare sweep width=10 KHz, pulse width=30 degrees, acquisition time=2 s,acquisition delay=5 s and number of scans=120. Chemical shifts aredetermined relative to the TCE-d2 signal which is set to 5.98 ppm.

The chain end unsaturations are determined as follows. The vinylresonances of interest are between from about 5.0 to 5.1 ppm (VRA), thevinylidene resonances between from about 4.65 to 4.85 ppm (VDRA), thevinylene resonances from about 5.31 to 5.55 ppm (VYRA), thetri-substituted unsaturated species from about 5.11 to 5.30 ppm (TSRA)and the aliphatic region of interest between from about 0 to 2.1 ppm(IA). The number of vinyl groups/1000 Carbons is determined from theformula: (VRA*500)/((IA+VRA+VYRA+VDRA)/2)+TSRA). Likewise, the number ofvinylidene groups/1000 Carbons is determined from the formula:(VDRA*500)/((IA+VRA+VYRA+VDRA)/2)+TSRA), the number of vinylenegroups/1000 Carbons from the formula(VYRA*500)/((IA+VRA+VYRA+VDRA)/2)+TSRA) and the number oftri-substituted groups from the formula(TSRA*1000)/((IA+VRA+VYRA+VDRA)/2)+TSRA). VRA, VDRA, VYRA, TSRA and IAare the integrated normalized signal intensities in the chemical shiftregions defined above.

GPC3D: Unless otherwise indicated, molecular weight (weight-averagemolecular weight, M_(w), number-average molecular weight, M_(n), andmolecular weight distribution, M_(w)/M_(n) or MWD, and branching index(g′vis)) are determined using a High Temperature Size ExclusionChromatograph (either from Waters Corporation or Polymer Laboratories),equipped with a differential refractive index detector (DRI), an onlinelight scattering (LS) detector, and a viscometer. Experimental detailsnot described below, including how the detectors are calibrated, aredescribed in: T. Sun, P. Brant, R. R. Chance, and W. W. Graessley,Macromolecules, Volume 34, Number 19, 6812-6820, (2001).

Three Polymer Laboratories PLgel 10 mm Mixed-B columns are used. Thenominal flow rate was 0.5 cm³/min, and the nominal injection volume is300 μL. The various transfer lines, columns and differentialrefractometer (the DRI detector) are contained in an oven maintained at135° C. Solvent for the SEC experiment is prepared by dissolving 6 gramsof butylated hydroxy toluene as an antioxidant in 4 liters of Aldrichreagent grade 1,2,4 trichlorobenzene (TCB). The TCB mixture is thenfiltered through a 0.7 μm glass pre-filter and subsequently through a0.1 μm Teflon filter. The TCB is then degassed with an online degasserbefore entering the SEC. Polymer solutions are prepared by placing drypolymer in a glass container, adding the desired amount of TCB, thenheating the mixture at 160° C. with continuous agitation for about 2hours. All quantities are measured gravimetrically. The TCB densitiesused to express the polymer concentration in mass/volume units are 1.463g/ml at room temperature and 1.324 g/ml at 135° C. The injectionconcentration ranges from 1.0 to 2.0 mg/ml, with lower concentrationsbeing used for higher molecular weight samples. Prior to running eachsample the DRI detector and the injector are purged. Flow rate in theapparatus is then increased to 0.5 ml/minute, and the DRI is allowed tostabilize for 8-9 hours before injecting the first sample. The LS laseris turned on 1 to 1.5 hours before running samples.

The concentration, c, at each point in the chromatogram is calculatedfrom the baseline-subtracted DRI signal, I_(DRI), using the followingequation:

c=K _(DRI) I _(DRI)/(dn/dc)

where K_(DRI) is a constant determined by calibrating the DRI, and(dn/dc) is the same as described below for the light scattering (LS)analysis. Units on parameters throughout this description of the SECmethod are such that concentration is expressed in g/cm³, molecularweight is expressed in g/mole, and intrinsic viscosity is expressed indL/g.

The light scattering detector used is a Wyatt Technology HighTemperature mini-DAWN. The polymer molecular weight, M, at each point inthe chromatogram is determined by analyzing the LS output using the Zimmmodel for static light scattering (M. B. Huglin, LIGHT SCATTERING FROMPOLYMER SOLUTIONS, Academic Press 1971):

$\frac{K_{o}c}{\Delta \; {R(\theta)}} = {\frac{1}{{MP}(\theta)} + {2A_{2}c}}$

Here, ΔR(θ) is the measured excess Rayleigh scattering intensity atscattering angle θ, c is the polymer concentration determined from theDRI analysis, A₂ is the second virial coefficient [for purposes of thisinvention and the claims thereto, A₂=0.0006 for propylene polymers and0.001 otherwise], P(θ) is the form factor for a monodisperse random coil(M. B. Huglin, LIGHT SCATTERING FROM POLYMER SOLUTIONS, Academic Press,1971), and K_(o) is the optical constant for the system:

$K_{o} = \frac{4\pi^{2}{n^{2}\left( {{dn}/{dc}} \right)}^{2}}{\lambda^{4}N_{A}}$

in which N_(A) is Avogadro's number, and (dn/dc) is the refractive indexincrement for the system. The refractive index, n=1.500 for TCB at 135°C. and X=690 nm. For purposes of this invention and the claims thereto(dn/dc)=0.104 for propylene polymers and 0.1 otherwise.

A high temperature Viscotek Corporation viscometer, which has fourcapillaries arranged in a Wheatstone bridge configuration with twopressure transducers, is used to determine specific viscosity. Onetransducer measures the total pressure drop across the detector, and theother, positioned between the two sides of the bridge, measures adifferential pressure. The specific viscosity, η_(s), for the solutionflowing through the viscometer is calculated from their outputs. Theintrinsic viscosity, [η], at each point in the chromatogram iscalculated from the following equation:

η_(s) =c[η]+0.3(c[η])²

where c is concentration and is determined from the DRI output.

The branching index, g′ (also referred to as g′vis), is calculated usingthe output of the SEC-DRI-LS-VIS method as follows. The averageintrinsic viscosity, [η]_(avg), of the sample is calculated by:

$\lbrack\eta\rbrack_{avg} = \frac{\sum{c_{i}\lbrack\eta\rbrack}_{i}}{\sum c_{i}}$

where the summations are over the chromatographic slices, i, between theintegration limits.

The branching index g′vis is defined as:

$g^{\prime} = \frac{\lbrack\eta\rbrack_{avg}}{k\; M_{v}^{\alpha}}$

where, for purpose of this invention and claims thereto, α=0.695 forethylene, propylene, and butene polymers; and k=0.000579 for ethylenepolymers, k=0.000262 for propylene polymers, and k=0.000181 for butenepolymers. My is the viscosity-average molecular weight based onmolecular weights determined by LS analysis.

All documents described herein are incorporated by reference herein forpurposes of all jurisdictions where such practice is allowed, includingany priority documents and/or testing procedures to the extent they arenot inconsistent with this text. As is apparent from the foregoinggeneral description and the specific embodiments, while forms of theinvention have been illustrated and described, various modifications canbe made without departing from the spirit and scope of the invention.Accordingly, it is not intended that the invention be limited thereby.Likewise, the term “comprising” is considered synonymous with the term“including.” Likewise whenever a composition, an element or a group ofelements is preceded with the transitional phrase “comprising,” it isunderstood that we also contemplate the same composition or group ofelements with transitional phrases “consisting essentially of,”“consisting of,” “selected from the group of consisting of,” or “is”preceding the recitation of the composition, element, or elements andvice versa.

What is claimed is:
 1. A catalyst system comprising a quinolinyldiamidotransition metal complex represented by the Formula I:

wherein: M is a Group 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 metal; J is athree-atom-length bridge between the quinoline and the amido nitrogen; Xis an anionic leaving group; L is a neutral Lewis base; R¹ and R¹³ areindependently selected from the group consisting of hydrocarbyls,substituted hydrocarbyls, and silyl groups; R², R³, R⁴, R⁵, and R⁶ areindependently selected from the group consisting of hydrogen,hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls,halogen, and phosphino; n is 1 or 2; m is 0, 1, or 2 n+m is not greaterthan 4; and any two adjacent R groups (e.g., R¹ & R², R² & R³, etc.) maybe joined to form a substituted hydrocarbyl, unsubstituted hydrocarbyl,substituted heterocyclic ring, or unsubstituted heterocyclic ring, wherethe ring has 5, 6, 7, or 8 ring atoms and where substitutions on thering can join to form additional rings; any two X groups may be joinedtogether to form a dianionic group; any two L groups may be joinedtogether to form a bidentate Lewis base; and an X group may be joined toan L group to form a monoanionic bidentate group; an activator; and anda metal hydrocarbenyl transfer agent.
 2. The catalyst system of claim 1,wherein J is selected from the following structures:

where

indicates connection to the complex.
 3. The catalyst system of claim 1,wherein the complex is further represented by Formula (II):

wherein M, L, X, m, n, R¹, R², R³, R⁴, R⁵, R⁶, and R¹³ are as defined inclaim 1, and E is carbon, silicon, or germanium; R⁷ through R¹² areindependently selected from the group consisting of hydrogen,hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls,halogen, and any two adjacent R groups may be joined to form asubstituted or unsubstituted hydrocarbyl or heterocyclic ring, where thering has 5, 6, 7, or 8 ring atoms and where substitutions on the ringcan join to form additional rings.
 4. The catalyst system of claim 3,wherein R¹¹ and R¹² are independently selected from hydrogen, methyl,ethyl, phenyl, isopropyl, isobutyl, and trimethylsilyl.
 5. The catalystsystem of claim 3, wherein E is carbon.
 6. The catalyst system of claim3, wherein R⁷, R⁸, R⁹, and R¹⁰ are independently selected from hydrogen,methyl, ethyl, propyl, isopropyl, phenyl, cyclohexyl, fluoro, chloro,methoxy, ethoxy, phenoxy, and trimethylsilyl.
 7. The catalyst system ofclaim 1, wherein M is Ti, Zr, or Hf.
 8. The catalyst system of claim 1,wherein R², R³, R⁴, R⁵, and R⁶ are independently selected from the groupconsisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, substitutedhydrocarbyls, and halogen.
 9. The catalyst system of claim 1, whereineach L is independently selected from Et₂O, MeOtBu, Et₃N, PhNMe₂,MePh₂N, tetrahydrofuran, and dimethylsulfide and each X is independentlyselected from methyl, benzyl, trimethylsilyl, neopentyl, ethyl, propyl,butyl, phenyl, hydrido, chloro, fluoro, bromo, iodo, dimethylamido,diethylamido, dipropylamido, and diisopropylamido.
 10. The catalystsystem of claim 1, wherein R¹ is 2,6-diisopropylphenyl,2,4,6-triisopropylphenyl, 2,6-diisopropyl-4-methylphenyl,2,6-diethylphenyl, 2-ethyl-6-isopropylphenyl, 2,6-bis(3-pentyl)phenyl,2,6-dicyclopentylphenyl, or 2,6-dicyclohexylphenyl; and/or R¹³ isphenyl, 2-methylphenyl, 2-ethylphenyl, 2-propylphenyl,2,6-dimethylphenyl, 2-isopropylphenyl, 4-methylphenyl,3,5-dimethylphenyl, 3,5-di-tert-butylphenyl, 4-fluorophenyl,3-methylphenyl, 4-dimethylaminophenyl, or 2-phenylphenyl.
 11. Thecatalyst system of claim 1, wherein J is dihydro-1H-indenyl and R¹ is2,6-dialkylphenyl or 2,4,6-trialkylphenyl.
 12. The catalyst system ofclaim 1, wherein R¹ is 2,6-diisopropylphenyl and R¹³ is a hydrocarbylgroup containing 1, 2, 3, 4, 5, 6, or 7 carbon atoms.
 13. The catalystsystem of claim 1, wherein the activator comprises an alumoxane and or anon-coordinating anion.
 14. The catalyst system of claim 1, wherein theactivator comprises one or more of: trimethylammoniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-diethylaniliniumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, trimethylammoniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(perfluorophenyl)borate, [Ph₃C⁺][B(C₆F₅)₄ ⁻], [Me₃NH⁺][B(C₆F₅)₄⁻],1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium,tetrakis(pentafluorophenyl)borate,4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine,triphenylcarbenium tetraphenylborate, and triphenylcarbeniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate.
 15. The catalyst system ofclaim 1, wherein the metal hydrocarbenyl transfer agent is representedby the formula:Al(R′)_(3-v)(R″)_(v) wherein each R′, independently, is a C₁-C₃₀hydrocarbyl group; each R″, independently, is a C₄-C₂₀ hydrocarbenylgroup having an allyl chain end; and v is from 0.01 to 3, preferablyv=2.
 16. The catalyst system of claim 15, wherein R″ is butenyl,pentenyl, hexenyl, heptenyl, octenyl or decenyl, and or R′ is methyl,ethyl, propyl, isobutyl, or butyl.
 17. The catalyst system of claim 1,wherein the metal hydrocarbenyl transfer agent comprises one or more oftri(but-3-en-1-yl)aluminum, tri(pent-4-en-1-yl)aluminum,tri(oct-7-en-1-yl)aluminum, tri(non-8-en-1-yl)aluminum,tri(dec-9-en-1-yl)aluminum, dimethyl(oct-7-en-1-yl)aluminum,diethyl(oct-7-en-1-yl)aluminum, dibutyl(oct-7-en-1-yl)aluminum,diisobutyl(oct-7-en-1-yl)aluminum, diisobutyl(non-8-en-1-yl)aluminum,dimethyl(dec-9-en-1-yl)aluminum, diethyl(dec-9-en-1-yl)aluminum,dibutyl(dec-9-en-1-yl)aluminum, diisobutyl(dec-9-en-1-yl)aluminum, anddiisobutyl(dodec-11-en-1-yl)aluminum.
 18. A polymerization processcomprising contacting one or more alkene monomers with the catalystsystem of claim
 1. 19. The process of claim 18, wherein the monomercomprises ethylene or propylene.
 20. The process of claim 18, whereinthe monomers comprise at least two of ethylene, propylene, and an alkyldiene.
 21. The process of claim 18, wherein the transition metal complexis supported.
 22. The process of claim 21, wherein the support issilica.
 23. The process of claim 18, wherein the polymerization isperformed in one or more continuous stirred tank reactors in series orin parallel.
 24. The process of claim 18, wherein the monomer comprisesethylene and octene.
 25. The process of claim 18, wherein the monomercomprises ethylene.
 26. A polymerization process comprising contactingone or more alkene monomers with the catalyst system of claim 3.